Journal of Environmental Management 314 (2022) 115101

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Journal of Environmental Management

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

Research article

APCS-MLR model: A convenient and fast method for quantitative

identification of nitrate pollution sources in groundwater
Lu Yu a, c, Tianyuan Zheng a, b, *, Ruyu Yuan a, b, Xilai Zheng a, b
a
College of Environmental Science and Engineering, Ocean University of China, Qingdao, 266100, China
b
Key Lab of Marine Environmental Science and Ecology, Ministry of Education, Ocean University of China, Qingdao, 266100, China
c
Ecological Environment Research and Development Center, Weihai Innovation Institute, Qingdao University, Weihai, 264200, China

A R T I C L E I N F O A B S T R A C T

Keywords: Nitrate (NO−3 ) contamination in groundwater has diverse sources and complicated transformation processes. To
Nitrate source effectively control NO−3 pollution in groundwater systems, quantitative and accurate identification of NO−3
Hydrochemical indicators sources is critical. In this work, we applied hydrochemical characteristics and isotope analysis to determine NO−3
Multivariate statistical model
source apportionment. For the first time, the NO−3 source contributions were calculated using hydrochemical
Bayesian isotope mixing model
indicators combined with multivariate statistical model (PCA-APCS-MLR). The results interpret that chemical
Method comparison
fertilizers (58.11%) and natural sources (22.69%) were the primary NO−3 sources in the vegetable cultivation
area (VCA) which were rather close to the estimation by Bayesian isotope mixing model (SIAR). In particular, the
contributions of chemical fertilizers in the VCA differed by only 3.79% between the two methods. Compared with
previous approaches e.g. SIAR, the key advantage of the proposed PCA-APCS-MLR model is that it only requires
the hydrochemical indicators which can be easily measured. A series of complicated experiments including
measurement of isotope data of NO−3 in groundwater, monitoring of in-situ pollution source information and
calculation of isotopic enrichment factor can be simply avoided. The PCA-APCS-MLR model offers a much more
convenient and faster method to determine the contribution rates of NO−3 pollution sources in groundwater.

1. Introduction
Groundwater nitrate (NO−3 ) pollution has become a significant
environmental problem worldwide, particularly in agricultural areas
(Rivett et al., 2008; Choi et al., 2017; Jia et al., 2018; Xin et al., 2019; Yu
et al., 2019). Excessively high NO−3 -N concentrations in groundwater
can cause serious health problems (when the groundwater is used as
drinking water) and negative environmental effect (such as eutrophi­
cation produced by the transport of NO−3 to the surface water) (Bastani
and Harter, 2019; Xin et al., 2021). As a result, the World Health Or­
ganization (WHO) has stipulated that the maximum NO−3 -N concentra­
tion threshold in groundwater for drinking water purposes is 11.3 mg/L.
In China, the groundwater quality standard (GB/T14848-2017) stipu­
lates that the concentration of NO−3 -N for drinking water shall not exceed
20 mg/L. However, in many agricultural regions and areas with inten­
sive human activity, the NO−3 concentrations in groundwater tend to
exceed drinking water standards (Burow et al., 2010; Kringel et al.,
2016; Motevalli et al., 2019; Yuan et al., 2020). Groundwater NO−3
sources are generally attributed to anthropogenic activities, with
intensive agriculture being a major source due to the use of chemical
fertilizers and animal manure, along with the discharge of sewage (Xue
et al., 2012; Gutierrez et al., 2018; Han et al., 2018; Lentz and Lehrsch,
2019). Accurate identification of NO−3 pollution sources is of great sig­
nificance for effective groundwater management.
The methods commonly used to determine the NO−3 sources mainly
include water quality analysis and stable isotope analysis (Cui et al.,
2018; Torres-Martinez et al., 2021). Principal component analysis (PCA)
is an important method for water quality analysis, having been widely
used for pollution source determination in aquatic systems (Wang et al.,
2017; Taufiq et al., 2019; Zhu et al., 2019). PCA extracts principal
components from water quality index parameters by reducing the
number of input variables, allowing potential pollution sources to be
identified qualitatively according to the major pollution factors extrac­
ted (Kim et al., 2015a; Matiatos, 2016; Meghdadi and Javar, 2018;
Torres-Martinez et al., 2021). However, PCA cannot estimate the pro­
portional contributions of pollution sources. Therefore, some studies
have utilized absolute principal component score (APCS) analysis
combined with multivariate linear regression (MLR), to further quantify

* Corresponding author. College of Environmental Science and Engineering, Ocean University of China, Qingdao, 266100, China.
E-mail address: zhengtianyuan@ouc.edu.cn (T. Zheng).

https://doi.org/10.1016/j.jenvman.2022.115101
Received 12 February 2022; Received in revised form 8 April 2022; Accepted 16 April 2022
Available online 23 April 2022
0301-4797/© 2022 Elsevier Ltd. All rights reserved.
L. Yu et al.
the impact of different pollution sources (Zhou et al., 2007; Su et al.,
2011; Gholizadeh et al., 2016; Jin et al., 2019; Rashid et al., 2020).
Currently, the APCS-MLR method has mainly been applied to air
pollution, heavy metals and organic pollution in water, but it has not yet
been used for NO−3 source apportionment in groundwater (Thurston and
Spengler, 1985; Meng et al., 2018; Chen et al., 2019a,b; Yan et al.,
2020). Therefore, the applicability and accuracy of the APCS-MLR
method for NO−3 source apportionment still requires further assess­
ment and verification. This will further expand and improve the appli­
cation of water quality analysis in quantitative source apportionment of
NO−3 .
As NO−3 pollution sources exhibit distinctive isotope signatures, ni­
trogen and oxygen isotope analysis and isotope mixing models have
been applied to identify NO−3 sources (Moore and Semmens, 2008;
Fenech et al., 2012; Denk et al., 2017; Guo et al., 2020). In particular, the
Bayesian isotope mixing model (SIAR) is increasingly being used for
NO−3 source apportionment, due to its consideration of the isotopic
fractionation effect (Xia et al., 2017; Liu et al., 2018; Li et al., 2019; Sui
et al., 2020; Zhang et al., 2020). However, the results of NO−3 source
apportionment are often uncertain due to the overlap in source isotope
compositions and the uncertainty of isotopic fractionation factors
(Nakagawa et al., 2017; Nikolenko et al., 2018; Biddau et al., 2019; Kruk
et al., 2020). Previous researchers have reviewed that the accuracy of
NO−3 source apportionment can be improved by using the isotopic values
of in-situ pollution sources and seeking suitable isotopic enrichment
factor (ϵ) (Zhang et al., 2018; Yu et al., 2020). However, a series of
complicated experiments are required to obtain sufficient isotope data of
Fig. 1. Location of the Dagu River groundwater reservoir and distribution of groundwater sampling sites with the land-use (a); typical geological profile of the
middle (a-a’) (b).
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Journal of Environmental Management 314 (2022) 115101
NO−3 in groundwater and in-situ pollutant sources, as well as to inves­
tigate the ϵ value of nitrogen transformation process. Therefore, it is
particularly critical to find a convenient and reliable quantitative anal­
ysis method of NO−3 pollution sources. In contrast, measurement of
conventional hydrochemical indicators is much more simple.
To address the above issues, in this work, we proposed the APCS-
MLR model which can accurately capture the NO−3 source apportion­
ment, while avoid all the complicated experiments. The objectives were
as follows: (1) to provide a convenient and fast method for the quanti­
tative identification of NO−3 pollution sources in groundwater (PCA-
APCS-MLR model); (2) to verify the feasibility and applicability of the
PCA-APCS-MLR model in quantitative identification of NO−3 pollution
sources by comparing with SIAR model. Through quantitative identifi­
cation of NO−3 sources from multiple perspectives, this study will provide
a useful tool for effective prevention and control of NO−3 pollution in
groundwater.
2. Materials and methods
2.1. Study area
The Dagu River groundwater source area (120◦ 04′ 48′′ – 120◦ 21′ 00′′
E, 36◦ 18′ 00′′ – 36◦ 45′ 45′′ N) is located in the middle and lower reaches
of the Dagu River (Qingdao, China), with an area of 460 km2 (Fig. 1a).
The groundwater in the study area is the main water source for agri­
cultural and industrial activities in the surrounding area. The ground­
water of Dagu River is mainly distributed in the sand and gravel layer
L. Yu et al.
from the Quaternary alluvial diluvium (Ke et al., 2021). The typical
vertical geological profile of Dagu River groundwater source area is
shown in Fig. 1b. The overlying layer of the aquifer is mainly clay sandy
soil and sandy clay with a thickness of 2–5 m. The phreatic aquifer is
mainly composed of coarse sand, medium coarse sand, and a little
gravel, with an average thickness of 5 m. The bottom layer is mainly
composed of Cretaceous clay rock and sandstone with poor perme­
ability, forms a good waterproof layer and is conducive to the storage of
groundwater (Fang et al., 2020). The groundwater of Dagu River is
recharged by precipitation, river infiltration, and irrigation, and
discharge occurs through artificial exploitation, runoff, and evaporation
(Nai et al., 2020).
The study area is an alluvial plain with a flat terrain. The region is a
typical agricultural planting area in Shandong Province (composed of
71% agricultural land). Based on field investigations, the study area can
be classified as vegetable cultivation area (VCA) and grain cultivation
area (GCA) (Fig. 1a) (Yu et al., 2020). Intensive agricultural activities,
especially in the VCA, have led to the use of large amounts of chemical
fertilizers. According to the Qingdao Statistical Yearbook in 2019, the
average amount of chemical fertilizer applied in Qingdao was 517
kg/hm2, which is about 4-fold higher than the global average. However,
some studies have reported that the agricultural utilization of nitrogen
fertilizers in China remains below 50% overall (Cai et al., 2018; Hu
et al., 2019). The N not absorbed by plants gradually accumulates in the
soil and is transformed into NO−3 by microorganisms, with NO−3 then
leaching into groundwater through unsaturated zones, resulting in the
accumulation of NO−3 in groundwater.
2.2. Sample collection and analysis
A total of 34 groundwater samples were collected from wells in
March 2019, including 24 VCA and 10 GCA groundwater samples
(Fig. 1a). 200 mL groundwater samples were collected from each sam­
pling site using a water sampler, with all samples filtered through 0.45
μm filters and stored at 4 ◦ C for hydrochemical analyses. About 50 mL
groundwater were filtered through 0.22 μm filters and stored in poly­
ethylene bottles at − 20 ◦ C for isotope analyses. More details about the
groundwater and pollution sources sampling and isotope testing were
provided by Yu et al. (2020).
Groundwater temperature, pH, electrical conductivity (EC), and
dissolved oxygen (DO) content were measured on site using a portable
multi-parameter water quality meter (HQ40d, Hach, US). The nitrogen
concentrations in groundwater samples were determined by spectro­
photometry (Unico 2800 UV/VIS). The detection method included ul­
traviolet spectrophotometry for NO−3 -N detection, the Nessler’s reagent
colorimetric method for ammonium (NH+ 4 -N) detection and ethyl­
enediamine colorimetry for nitrite (NO−2 -N) detection. The metal cations
potassium (K+), sodium (Na+), calcium (Ca2+), magnesium (Mg2+), and
anions chloride (Cl− ) and sulfate (SO2−
4 ) were measured using ion
chromatography (ICS-3000, Dionex, US). Bicarbonate (HCO−3 ) concen­
trations were determined by acid-base titration. The total hardness of
water was calculated based on the Ca2+ and Mg2+ concentrations. The
total dissolved solids (TDS) concentration was calculated as the com­
bined content of ions minus half of the concentration of HCO−3 .
2.3. Single pollution index method
The single pollution index method was used to evaluate water
quality, which is expressed according to Equation (1) as follows (Men
et al., 2018):
PI = Ci /Ci0 (1)
where, PI is the pollution index; Ci is the measured value of the water
quality indicator i; Ci0 is the evaluation standard value for water quality
indicator i, based on the standard defined by level III of the Chinese
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Journal of Environmental Management 314 (2022) 115101
groundwater quality standard for drinking water (GB/T14848-2017). If
the Pi > 1, then the water quality index i value exceeds the standard limit
and the water is considered polluted, with larger Pi values indicating a
more serious degree of pollution (Wang et al., 2020).
2.4. Multivariate statistical model
2.4.1. Principal component analysis (PCA)
Principal component analysis (PCA) can extract principal compo­
nents (PCs) from multiple index parameters by reducing the dimension
of multivariate datasets (Singh et al., 2005). The main steps in PCA
identification of pollution sources include: (1) assessing the feasibility of
original indicators for factor analysis; (2) reducing the dimension of
variables and determining the number of PCs; (3) obtaining a rotation
factor loading matrix to analyze the rationality of the extracted results;
(4) identifying the pollution sources based on the PCs (Chen et al.,
2019a,b; Yuan et al., 2020).
The number of PCs is determined by analysis of their eigenvalue (>1)
(Liu et al., 2019; Yan et al., 2020). Larger variance contribution rates
indicate that PCs have a stronger ability to explain the original data.
Factor loadings reflect the relative importance of each variable in PCs,
with factor loading values of >0.75, 0.75–0.5 and 0.5–0.3 defined as
strong, medium and weak, respectively (Xiao et al., 2016; Liu et al.,
2019).
2.4.2. Absolute principal component score (APCS) - multivariate linear
regression (MLR)
The absolute principal component score (APCS) was determined on
the basis of PCA results, with multivariate linear regression (MLR)
performed using measured pollutant concentrations as the dependent
variable and APCS values as the independent variable (Su et al., 2011;
Gholizadeh et al., 2016). The contribution of different pollution sources
was determined according to regression coefficient values. The
APCS-MLR model can be expressed using Equations (2)–(5) as follow
(Huang et al., 2018; Yan et al., 2020):
(0 − xi ) − xi
(Z0 )i = = (2)
σi σi
∑
I
(A0 )p = Spi (Z0 )i (3)
i=1
APCSjp = (Az )jp − (A0 )p (4)
∑
P
Ci = bi + bpi × APCSjp (5)
p=1
where, (Z0)i indicates the normalized concentration of indicator i in an
anthropogenic sample, where its concentration is 0; xi indicates the
average concentration of indicator i in all samples; σi indicates the
standard deviation of all samples for indicator i; (A0)p indicates the
principal component score in a “zero” polluted sample; Spi indicates the
scoring coefficient of indicator i in the principal component p; APCSjp is
the APCS of sample j in principal component p; (Az)jp indicates the
principal component score of sample j in principal component p; Ci in­
dicates the concentration of indicator i; bi indicates a constant multiple
regression term; bpi indicates the regression coefficient of principal
component p for indicator i.
In the APCS-MLR model, bpi × APCSjp is used to assess the contri­
bution of principal component p to indicator i in sample j. In this study,
the average value of bpi × APCSjp was established for all samples as the
contribution of each source to NO−3 pollution (Ma et al., 2018; Yan et al.,
2020).
L. Yu et al.
2.5. Bayesian isotope mixing model (SIAR)
In this study, the Bayesian isotope mixing model (SIAR) was also
used to determine the NO−3 sources apportionment, expressed as follows
(Parnell et al., 2010):
∑K ( )
Xij = k=1
Pk Sjk + εjk + νij
( )
Sjk ∼ N μjk , ω2jk
( )
εjk ∼ N λjk , τ2jk
( )
vjk ∼ N 0, σ 2j
where Xij is the isotopic value j of sample i; Sjk is the source value k of
isotope j; Pk is the proportion of source k, which needs to be estimated by
the SIAR model; ϵjk is the enrichment factor of isotope j on source k; and
νij is the residual error. In this study, the SIAR model was performed with
the SIAR package in the R Programming Language (R version ×64
3.4.2).
2.6. Statistical analysis
Correlation analysis, PCA and multiple linear regression were carried
out using IBM SPSS version 25.0. The correlation between different in­
dicators were analyzed by Pearson’s correlation coefficients, with sta­
tistical significance at the p < 0.05 level. Kaiser-Meyer-Olkin (KMO) and
Bartlett spherical tests were used to further analyze the correlation be­
tween indicators (Zhang et al., 2010; Meghdadi and Javar, 2018). KMO
values closer to 1 represent stronger correlations between indicators and
therefore higher accuracy factor analysis outcomes. Only KMO value >
0.5 and Bartlett spherical tests at the p < 0.05 level is suitable for factor
analysis and principal component analysis (Gholizadeh et al., 2016).
3. Results and discussion
3.1. Groundwater pollution assessment
The hydrochemical parameter statistics for all groundwater samples
are summarized in Table S1. The water quality in the study area was
evaluated according to level III of the Chinese groundwater quality
standard (GB/T14848-2017) for drinking water (Table S2). As shown in
Fig. 2a, the most serious pollutants were NO−3 -N and total hardness, with
88.2% (30 samples) of groundwater samples exceeding the groundwater
quality standard limits. Concentrations of SO2− 4 and TDS exceeded the
standard limits in 32.4% (11 samples) of groundwater samples, while
Fig. 2. Rate of standard limit exceedance in groundwater samples (a) and average pollution index values (b) for the assessed pollutants.
Journal of Environmental Management 314 (2022) 115101
Cl− , NH+
4 -N, pH, and Na exceeded the standard limits in 14.7%, 11.8%,
+
5.9%, and 2.9% of samples, respectively. Results indicate that most
groundwater in the study area was seriously polluted by NO−3 and that
the level of groundwater hardness was high.
From the perspective of cropping system, the groundwater quality in
the study area exhibited distinct spatial differences, especially in terms
of NO−3 pollution, which was more serious in the VCA than in the GCA
(Fig. 2b). In the VCA, the average NO−3 PI value was 3.8 and the
(6) maximum PI value was 8.63. In the GCA, the average NO−3 PI value was
1.3 and the maximum PI value was 3.2. The average PI values for TDS,
SO2−
4 , Cl , Na , and NH4 -N did not exceed 1, suggesting that these in­
− + +
dicators did not cause significant pollution within the study area, while a
low level of local pollution was present. Results indicate that NO−3 was
the dominant contaminant in the groundwater sources of the Dagu
River.
3.2. Hydrochemical characteristics
The hydrochemical characteristic of groundwater in the study area
are shown in the Piper’s diagram (Fig. 3). The cation in groundwater
samples was mainly Ca2+. The percentages of Ca2+ milligram equivalent
in most sampling sites were more than 50%, with no significant spatial
divergence observed between different cropping systems. Combined
cation and anion analysis showed that two hydrochemical types were
identified, including Ca–HCO3 (Cl + NO3) and Ca–SO4 (Cl + NO3). The
Ca– HCO3 (Cl + NO3) type was mainly distributed in the GCA, while the
Ca–SO4 (Cl + NO3) type was mostly distributed in the VCA, indicating
that the cropping system significantly influenced the groundwater
chemical composition.
Studies have reported that Ca–HCO3 type ions are mainly derived
from the dissolution of carbonate rocks, while Ca− (Cl + NO3) and
Ca–SO4 (Cl + NO3) ions mainly originate from anthropogenic activities,
such as chemical fertilizer utilization and wastewater discharge (Kim
et al., 2015b; Wang et al., 2017). Therefore, the hydrochemical
composition of groundwater in the GCA was affected by both natural
and anthropogenic activities, while the in the VCA it was mainly influ­
enced by anthropogenic activities, especially the extensive use of fer­
tilizers containing potassium sulfate, resulting in the increase in SO2−
4
concentrations.
3.3. Source apportionment using the PCA-APCS-MLR model
3.3.1. Identification of potential pollution sources using PCA
Based on the results of correlation analysis, the indicators DO, K+,
Na+, Ca2+, Mg2+, Cl− , SO2− 4 , and NO3 were used for PCA. In the VCA,
−
the KMO (0.71) and Bartlett’s test (p < 0.001) results confirmed the
suitability of the dataset for PCA (Gholizadeh et al., 2016; Meghdadi and
4
L. Yu et al. Journal of Environmental Management 314 (2022) 115101

Fig. 3. Piper’s diagram showing the hydrochemical types of groundwater samples.

Javar, 2018). However, in the GCA, the KMO value of 0.43 indicated
that data was not suitable for PCA analysis due to the small number of
sampling sites. Therefore, this study only carried out source appor­
factor loading, allowing pollution sources to be inferred. For the VCA
(Fig. 4), in PC1, Na+ and Mg2+ exhibited strong loads, while Cl− , K+ and
SO2−
4 exhibited medium loads. The correlation coefficients of Na with
+

tionment for the VCA.
The extraction results of PCs in the VCA were listed in Table S3. In
the VCA, two PCs were extracted with eigenvalues of >1 and a cumu­
lative variance percentage of 76.98%, indicating that these PCs could
adequately explain most of the information in the original dataset (Liu
et al., 2019; Yan et al., 2020). After the factor loading matrix was rotated
using the maximum variance method, PC1 and PC2 explained 39.70%
and 37.28% of the total variance, respectively.
The dominance of each indicator on the PCs was obtained by rotating
Mg2+ and Cl− were all >0.75 (p < 0.01), indicating that these ions
originate from the same pollution source. For the conventional
groundwater ions, they were mainly derived from the dissolution of
natural minerals (Wang et al., 2017). K+ is easily adsorbed by clay and
utilized by plants, resulting in low groundwater concentrations and
therefore, K+ was also considered to originate from natural minerals.
SO2−
4 is usually attributed to the dissolution of sulfate sediments and the
oxidation of sulfur minerals under natural conditions (Matiatos, 2016).
However, SO2− 4 concentrations in some sampling sites exceeded the

Fig. 4. Rotation factor loading for the vegetable cultivation area.

5
L. Yu et al.
groundwater standard limit, which was likely to be caused by the use of
K2SO4 compound fertilizer. In summary, PC1 was mainly formed from
natural sources, with an additional contribution from chemical fertil­
izers in areas with excessive SO2−4 levels.
In PC2, Ca2+, NO−3 -N and DO exhibited strong loadings (Fig. 4). The
concentration of NO−3 -N in the natural state usually does not exceed 3
mg/L, which is considered the threshold for contribution from anthro­
pogenic activity (Ogrinc et al., 2019). However, the evaluation results
(section 3.1) indicate that the degree of NO−3 pollution in the study area
was serious and therefore, it can be concluded that NO−3 mainly derived
from anthropogenic activities. Generally, Ca2+ in groundwater origi­
nates mainly from the weathering and dissolution of sediments. How­
ever, a significant positive correlation was observed between Ca2+ and
NO−3 -N with a regression coefficient of 0.79 (p < 0.01), indicating that
Ca2+ may also be derived from anthropogenic activities (Rashid et al.,
2018; Jehan et al., 2019). According to the field investigations, vege­
table planting usually requires a large amount of nitrogen fertilizers,
such as urea and ammonium nitrogen fertilizer. After NH+ 4 enters the
2+ 2+
soil, ion exchange occurs between NH+ 4 and Ca , with Ca extracted
from the soil leaching into groundwater. H+ produced by the trans­
formation of NH+ 4 to NO3 could enhance the leaching of soluble calcium,
−
leading to an increase in Ca2+ concentrations in groundwater. In addi­
tion, as vegetable crops commonly require calcium for growth, calcium
fertilizers are widely used, further increasing the Ca2+ content in
groundwater. The average concentration of DO in the VCA was 6.67
mg/L, suggesting that there was no obvious organic pollution input in
this area (Gholizadeh et al., 2016). Therefore, PC2 was attributed to
chemical fertilizer pollution sources.
3.3.2. Determination of pollution source contributions
Based on PCA, natural sources (NS) and chemical fertilizers (CF)
were determined to be the dominant NO−3 sources in the VCA. The
regression equation described in Equation (7) was obtained using APCS-
MLR model:
C = 11.85 × APCS1 + 36.26 × APCS2 − 39.20 (P < 0.05) (7)
2
The adjusted regression coefficient (A-R ) was equal to 0.808, indi­
cating that the model fitted well and could explain 80.8% of the NO−3
source contributions, while the remaining 19.2% was attributed to
multiple mixed sources (MMS) (Gholizadeh et al., 2016; Yan et al.,
2020).
The contributions of NO−3 sources established by the APCS-MLR
model showed that the dominant NO−3 source was CF in the VCA, ac­
counting for 58.11%. This finding was consistent with the monitoring
result from field investigation, finding that intensive vegetable cultiva­
tion results in the use of large amounts of chemical fertilizers. The sec­
ond major source was NS (mineralization of soil organic nitrogen),
which accounted for 22.69% of NO−3 pollution sources. Since NS also
includes a small CF contribution (in areas with excessive SO2−
4 ), the
overall contribution of CF may be underestimated in the results of this
study.
3.4. Source apportionment by SIAR model
In this study, δ15N and δ18O were used to calculate the contribution
of four potential pollution sources (CF, NS, atmospheric deposition
(AD), and manure and sewage (M&S)). The δ15N-NO−3 and δ18O-NO−3 of
groundwater samples were shown in Table S4. The isotopic values of the
in-situ pollution sources and the ϵ in the Dagu River groundwater source
area were obtained from the literature of Yu et al. (2020, 2021)
(Table 1).
According to the operation results of SIAR model, the source con­
tributions under different cropping systems were shown in Fig. 5. Pre­
vious studies (Yu et al., 2020) have shown that nitrogen transformation
and isotopic fractionation occurred during NO−3 pollution in the study
area. Considering the nitrogen isotopic fractionation effect, in the VCA,
6
Journal of Environmental Management 314 (2022) 115101
Table 1
δ15N and δ18O values and isotopic enrichment factor (ϵ) of various pollution
sources.
Source δ15N (‰) δ18O (‰)
Mean SD ϵ Mean SD ϵ
AD − 4.56 1.19 0 64.75 5.99 0
NS 4.48 0.7 − 8.7 ± 2.7 2.85 0.16 0
CF − 0.29 1.96 − 8.7 ± 2.7 2.85 0.16 0
M&S 2.52 1.92 14.7 ± 2.8 2.85 0.16 0
Fig. 5. Contributions of NO−3 sources established by SIAR model in the vege­
table cultivation area (VCA) and grain cultivation area (GCA).
the NO−3 pollution mainly came from CF (54.32%) and NS (37.75%),
followed by M&S (6.63%) and AD (1.3%). In the GCA, NS (33.67%), CF
(33.27%), and M&S (30.16%) were the main contributors to NO−3
pollution, while AD contributed only 2.90%. The contribution pro­
portions of CF and M&S showed significant spatial variation under
different cropping systems, while the difference of NS and AD was not
obvious. This was because intensive vegetable cultivation required more
fertilizer than grain cultivation (Min et al., 2011). The survey found that
CF was the most widely used fertilizer in vegetable planting due to its
quick and efficient effect. Land use type (Fig. 1a) indicated that resi­
dential areas in the GCA were more concentrated than in the VCA. The
residential areas were dominated by rural and town with imperfect
sewage treatment facilities, resulting in the increase of M&S contribu­
tions in the GCA.
The application of ϵ significantly changed the contributions of NO−3
pollution sources, especially in the VCA (Fig. 5). Due to isotopic frac­
tionation effect, in the VCA, the contribution of NS increased by 23.70%,
while the contribution of CF and M&S decreased by 6.74% and 17.03%,
respectively. In the GCA, the contribution of NS increased by 9.10%,
while the contribution of CF and M&S decreased by 7.24% and 1.65%,
respectively. The accuracy of NO−3 source apportionment could be
improved by determining and applying the ϵ according to the trans­
formation processes of different nitrogen sources (Yu et al., 2020).
However, to investigate the ϵ of nitrogen transformation processes will
increase the workload and consume more time and money, which makes
NO−3 source apportionment more complicated.
3.5. Comparison of source apportionment methods
To verify the validity and feasibility of the PCA-APCS-MLR model,
this study analyzed and compared NO−3 source apportionment results
from the perspectives of hydrochemical characteristics and isotopes. The
contributions of NO−3 sources in the VCA were determined by APCS-MLR
and SIAR models respectively, as shown in Fig. 6. In the VCA, the results
of both source apportionment methods showed that CF and NS were the
main sources of NO−3 pollution. However, the APCS-MLR model failed to
identify M&S. The results of SIAR model indicated that M&S contributed
was only 6.63%. The low contribution was the main reason for the
L. Yu et al.
Fig. 6. Comparative analysis of nitrate pollution sources in the vegetable
cultivation area using different source apportionment methods.
difficulty in identification, leading to the inclusion of M&S in MMS in
the APCS-MLR model. Another reason was that few indicators were
selected for principal component analysis, which could not fully reflect
the water quality characteristics, leading to difficulty in identifying
some pollution sources. Therefore, when the PCA-APCS-MLR model is
used for NO−3 source apportionment, more hydrochemical indicators
should be determined, such as chemical oxygen demand (COD), phos­
phate (PO3− 4 ), total coliform group and bacterial count. This will help
extract more representative principal components and improve the
comprehensiveness of pollution source identification.
Although the results generated using the two methods differed to
some degree, they were largely consistent. In particular, the identified
contribution of CF pollution sources in the VCA differed by only 3.79%
between the two methods. The PCA-APCS-MLR model has the advantage
of not needing detailed information on pollution sources, requiring only
hydrochemical indicators to extract the PCs and infer pollution sources,
which can save cost and time. The SIAR model can estimate the
contribution of pollution sources using the isotopic characteristics of
groundwater and pollution sources. However, overlap in the isotopic
characteristics of different sources and the complexity of isotopic frac­
tionation, can reduce the accuracy of source apportionment (Nikolenko
et al., 2018; Biddau et al., 2019; Yu et al., 2020). In conclusion,
compared with SIAR model, the PCA-APCS-MLR model is a simpler and
faster method for quantitative identification NO−3 pollution sources in
groundwater. The PCA-APCS-MLR model can be extended to determine
NO−3 pollution sources in different areas. However, it should be noted
that water quality indicators related to possible pollution sources need
to be monitored in different areas. For example, heavy metals (plum­
bum, cadmium, chrome, etc.), phenols and petroleum hydrocarbons
pollutants should also be monitored in industrial areas, while COD,
3−
NH+ 4 , PO4 , surfactant, total coliform group and bacterial count should
be monitored in livestock farming areas or urban areas.
4. Conclusions
Nitrate has become the dominant contaminant in the Dagu River
groundwater source area. In this study, NO−3 sources and their propor­
tional contributions were determined using hydrochemical indicators
and isotopic characteristics. This is the first study to compare the results
generated using a multivariate statistical model and a Bayesian isotope
mixing model for NO−3 source apportionment. These findings will benefit
the development of NO−3 source apportionment models, while also
providing useful information for the reduction of NO−3 contamination in
groundwater. The main conclusions are as follows:
7
Journal of Environmental Management 314 (2022) 115101
(1) According to the PCA-APCS-MLR model, CF and NS were the
primary contributors to NO−3 contamination in the VCA, with
contributions of 58.11% and 22.69%, respectively. Therefore,
optimizing the fertilization mode and reducing the loss of nitro­
gen fertilizer are the key to control the NO−3 pollution in the
intensive vegetable cultivation area.
(2) The results of NO−3 source apportionment determined by the PCA-
APCS-MLR model were close to those estimated by the SIAR
model in the VCA. In particular, the contributions of CF differed
by only 3.79% between the two methods. The main disagreement
between the two methods was the effective identification of M&S.
Future research can examine representative indicators of M&S to
improve the PCA-APCS-MLR model applications.
(3) The PCA-APCS-MLR model offers a convenient and fast method
for the quantitative identification of NO−3 pollution sources in
groundwater. The major advantage of this model is that it avoids
obtaining isotope data and isotopic enrichment factor, which
greatly reduces the experimental time and cost, and improves the
simplicity of NO−3 source apportionment. The hydrochemical in­
dicators are the only required information which can be easily
measured.
Author statement
Lu Yu: Conceptualization, Methodology, Software, Validation,
Formal analysis, Writing - original draft, Writing - review & editing,
Visualization. Tianyuan Zheng: Resources, Supervision, Project admin­
istration, Writing - review & editing. Ruyu Yuan: Investigation, Data
curation. Xilai Zheng: 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 influence
the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (grant number 41731280), the Joint Funds of National Natural
Science Foundation of China - Shandong Province (grant number
U1806210), the National Natural Science Foundation of China (grant
number 51978348).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jenvman.2022.115101.
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