Environ Geochem Health
https://doi.org/10.1007/s10653-021-01011-z (0123456789().,-volV)
(0123456789().,-volV)
ORIGINAL PAPER
Assessment of the hydrochemistry, water quality,
and human health risk of groundwater in the northwest
of Nansi Lake Catchment, north China
Zongjun Gao . Cong Han . Shuyu Yuan . Jiutan Liu . Yuming Peng .
Changsuo Li
Received: 3 December 2020 / Accepted: 9 June 2021
Ó The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract In this study, the formation mechanism
and water quality of groundwater in the northwest of
Nansi Lake Catchment (NNLC) were analyzed
through mathematical statistics, hydrochemical anal-
ysis and entropy weighted water quality index
(EWQI), and the human health risk of nitrate was
also evaluated. To this end, 89 wells in the NNLC were
sampled, and the groundwater samples were divided
into three groups (I, II, and III) according to cluster
analysis results and spatial distribution. The main
results are as follows: Topographically, Groups I, II,
and III correspond to the alluvial plains, apron plain,
and low hills and its front margin, respectively.
According to the Piper diagram, the hydrochemical
types of Groups I and II groundwater are Na–SO4Cl
and CaMg–HCO3, respectively, and that of Group III
is more concentrated, mostly corresponding to the Ca–
Z. Gao  C. Han  S. Yuan
College of Earth Science and Engineering, Shandong
University of Science and Technology, Qingdao 266590,
China
J. Liu (&)
College of Energy and Mining Engineering, Shandong
University of Science and Technology, Qingdao 266590,
China
e-mail: ljtsdust@126.com
Y. Peng  C. Li
801 Institute of Hydrogeology and Engineering Geology,
Shandong Provincial Bureau of Geology & Mineral
Resources, Jinan 250014, China
HCO3 type. Hydrochemical analysis indicated that the
development of groundwater hydrochemistry is
mainly attributable to water–rock interactions, with
the primary process being the dissolution of minerals
such as calcite, dolomite, gypsum, and albite. Evapo-
ration exhibited an increasing trend from the northeast
to the southwest. Groups I and III presented obvious
effects of human activities, with Group I showing
sulfate pollution and Group III mainly showing nitrate
pollution. Analysis of the characteristics and causes of
the groundwater hydrochemistry revealed the pro-
posed approach has excellent performance for classi-
fication in areas with complex hydrogeological
conditions. The results of EWQI showed that the
overall water quality was good, following the order
Group III [ Group II [ Group I. The overall human
health risk of nitrate in groundwater was low, but the
Y. Peng  C. Li
Key Laboratory of Groundwater Resources and
Environment, Shandong Provincial Bureau of Geology &
Mineral Resources, Jinan 250014, China
Y. Peng  C. Li
Shandong Engineering Research Center for Groundwater
Environmental Protection and Remediation,
Jinan 250014, China
123

risk was slightly higher for children than for adults.
Therefore, the effects of nitrate contamination should
be considered when exploiting hilly and peri-urban
groundwater for drinking water.
Keywords Groundwater  Hydrochemistry  Water
quality  Human health risk  The northwest of Nansi
Lake Catchment
Introduction
As a clean, abundant, and easily exploitable source of
water, groundwater has played an invaluable role in
the development of the human society for thousands of
years. However, with the increasing demand for
natural resources accompanying the development of
modern technology and skyrocketing population den-
sities, the natural environment, including groundwa-
ter, is being significantly affected. The development of
land has changed the ecological environment. In
addition, industrial and agricultural production activ-
ities and urban sewage discharge have polluted
groundwater (He et al., 2020; Sener et al., 2020).
Pollution can change the groundwater chemistry,
which has important implications for human health.
Today, with the continuous pollution of groundwater,
the hazards are becoming apparent and beginning to
affect human health (Wu & Sun, 2015). The formation
of groundwater chemistry is complex, involving
natural influences, such as regional lithology, topo-
graphic features, and precipitation, in addition to
anthropogenic influences (Madhav et al., 2020;
Vaiphei et al., 2020).
In recent years, the natural and anthropogenic
causes of groundwater chemistry have been exten-
sively studied, and many methods have been proposed,
improved, and used in an integrative manner (Kim
et al., 2020; Valappil et al., 2020). Liu et al. (2020a)
combined multivariate statistical techniques and geo-
chemical simulations to reverse engineer the geo-
chemical evolution of groundwater in the Yellow
River irrigation region of China and investigate the
influence of anthropogenic factors. Abdul-Wahab
et al. (2020) applied principal component analysis
(PCA), geostatistical methods, and isotopes to analyze
the chemical and material sources of groundwater in
the Lower Anayari catchment, Ghana. By analyzing
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Environ Geochem Health
differences in the chemical composition of surface
water and groundwater as well as changes from the dry
to wet seasons, Liu et al. (2020a) investigated the
formation and evolution of groundwater chemotypes
holistically and evaluated the water quality and health
risks. Previous studies have shown that the sustainable
use of groundwater and prevention of groundwater
pollution can be achieved through the analysis and
characterization of groundwater chemistry, determi-
nation of the formation and evolution mechanism,
scientific evaluation of groundwater quality, and
human health risk assessment of pollutants (Jandu
et al., 2021; Mandal et al., 2021).
Nansi Lake is the second largest lake in the North
China Plain, and the surrounding area is flat and
densely populated. The northwest of Nansi Lake
Catchment (NNLC) is located in the transition zone
between the Taiyi Mountain and Yellow River alluvial
plain with complex geological conditions. In the
NNLC, groundwater is widely used for agricultural,
industrial, domestic, and drinking purposes, and
anthropogenic activities inevitably lead to groundwa-
ter pollution (Liu et al., 2020d). The geomorphological
characteristics of the study area and the types of
human activities have obvious regional differences,
and the chemical characteristics of groundwater in
different regions may also differ as a result. Thus far,
the water chemistry of the surface waters of four
southern lakes has been well studied, but groundwater
in the surrounding area has rarely been investigated.
Xu et al. (2020) used the fuzzy comprehensive
evaluation method and principal component analysis
to evaluate the water quality of surface waters in the
south Sihu Lake Basin, and extracted four principal
components: heavy metals, organic and toxic pollu-
tants, total nitrogen, and COD. Liu et al. (2020e)
characterized groundwater chemistry and assessed the
health risk of fluorine elements in the southwest plain
of Shandong Province, which includes the NNLC. Liu
et al. (2021) conducted a qualitative and quantitative
analysis of the relationship between water pollution
and economic growth in the NNLC and pointed out
that domestic sewage discharge is continuously
increasing and has been one of the main sources of
pollution. Gao et al. (Gao et al., 2019a) analyzed the
chemical characteristics of groundwater and evaluated
its suitability for irrigation in the western part of the
southwest plain of Shandong Province, where the
groundwater is of Na–HCO3 type and mixed type, and
Environ Geochem Health
concluded that this area experiences the dissolution of
calcite, dolomite, gypsum and other minerals. For a
study area containing multiple geological units,
determining the spatial correspondence between geo-
logical units and identifying groundwater types are of
high significance. For this purpose, the extraction of
important information hidden in the raw data popula-
tion and determination of complex interconnections
between water chemistry samples or indicators are
important issues that remain to be resolved.
This study attempted to address the abovemen-
tioned issues. The main objectives of this study were
to (1) verify the practicability and research value of the
combination of cluster analysis (CA) and spatial
distribution for the grouping of groundwater chem-
istry, which can contribute to hydro-chemical analysis
in areas with complex hydrogeological conditions; (2)
determine the chemical characteristics, causes, and
controlling factors of groundwater in the northwestern
part of the NNLC; (3) assess groundwater quality and
determine the human health risk of nitrates. The
research results can provide reference for the devel-
opment and protection of groundwater resources in the
NNLC area, as well as other similar areas in the world.
Study area
The northwest of Nansi Lake Catchment (NNLC)
belongs to the administrative division of Jining City in
the southwest of Shandong Province, China (Fig. 1). It
is bordered by the Yellow River in the north, Nansi
Lake in the south, the Taiyi hills in the east, and the flat
Yellow River floodplain in the west. NNLC is located
34° 260 –35° 570 N, 115° 520 –117° 360 E, with a
north–south length of 167 km, east–west width of
158 km, and a total area 11,285 km2. The NNLC
belongs to the warm-temperate monsoon continental
climate zone, with four distinct seasons alternating
between warm and wet and an average annual
temperature of 13.8 °C; the average annual precipita-
tion is 689.2 mm, with the regional distribution of
precipitation decreasing from southeast to northwest.
Precipitation from June to September during the rainy
season accounts for more than 70% of the annual
precipitation. The main source of water vapor is the
intrusion of warm air masses from the western Pacific
low latitudes. The NNLC belongs to the Huai River
Basin, and Nansi Lake is the collective name of four
connected lakes: Weishan Lake, Zhaoyang Lake,
Dushan Lake, and Nanyang Lake. The Beijing-
Hangzhou Grand Canal runs north–south across the
four lakes, and the major rivers in the study area, such
as the Si River, Guangfu River, Su-Zhao-Xin River
and Dongyu River, are all connected to the four lakes
(Liu et al., 2020e).
The NNLC is located in the North China Plain at the
intersection of the low hills in the middle of Shandong
and the Yellow River Alluvial Plain in the southwest
of Shandong. Geologically, the NNLC belongs to the
depression of the southwest fracture of Shandong
Province in North China, and the terrain is high in the
east and low in the west, high in the north and low in
the south. The study area is - 31.5 to 648.8 m above
sea level, and the terrain is mainly plain, with the
ground elevation in the plain area ranging from 35 to
60 m above sea level, while the hilly area accounts for
only 19.5% of the total area. The bedrock in the study
area is hidden under the Quaternary system. Quater-
nary alluvial and proluvial deposits are widely spread
in the entire area. Lake-phase sediments are only
present in parts of the region (Liu et al., 2021). The
thickness of Quaternary sediments widely varies. The
lithology of the Pleistocene (Qp) deposit in the study
area is mainly brown and yellowish brown powdery
clay and clay, and the bottom is rich in calcareous
nodules and oblate iron-manganese nodules. The
Holocene (Q4) deposit overlies the Pleistocene, and
the lithology is mainly light yellow, grayish yellow
clay and silt clay, with thickness ranging from 2.3 to
9.8 m; silt lenses can be found locally, and a layer of
grayish green, grayish black silt clay or silt clay, rich
in organic matter at the bottom.
In the study area, shallow groundwater is found
mainly in Quaternary pore aquifers. Stratigraphic
thickness gradually increases from east to west in the
alluvial plain in the eastern part of the study area,
generally 30–100 m in the east and 150–250 m in the
western frontier zone. The aquifer particles range from
coarse to fine, and the lithology mainly consists of
alluvial and flooded yellow clay, sandy clay, sand, and
gravel. Water abundance gradually declines from the
northeast to the southwest, with single well gushes
dropping from 3000 to 1000m3/d. In the Yellow River
alluvial plains west of Nansi Lake, the thickness of the
quaternary aquifer is generally 200–300 m, and the
lithology is composed of sandy clay, silt and sub-sand.
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 Environ Geochem Health

Fig. 1 Geographical locations of the NNLC and sampling sites

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Environ Geochem Health

Materials and methods Various software were implemented to obtain the

water chemistry data of the collected samples, and
Sampling and analytical investigation descriptive statistical analysis was performed using
SPSS 22. The Piper diagram was produced using
Eighty-nine groundwater wells (Fig. 1) located in the AqQA software with the concentration of 7 main ions,
NNLC were sampled in May 2017. Groundwater Gibbs plots and various ion ratios were produced from
samples were collected from relatively shallow qua- the scatter plot of Origin 2019. Spatial distribution
ternary pore water from wells with depths of mostly plots based on inverse distance weighting interpola-
less than 100 m. The coordinates of each sampling tion were obtained from ArcGIS 10.2 (Liu et al.,
point were identified and recorded using GPS. Dried 2021).
and sterilized polyethylene plastic bottles with a
capacity of 5 L were used to collect and store samples. Entropy-weight water quality index (EWQI)
Sampling bottles were rinsed 2 to 3 times with
groundwater and then sampled. After sampling, the The water quality of groundwater was evaluated based
bottles were sealed and transported to the laboratory on the entropy-weight water quality index (EWQI).
for water quality testing as soon as possible under a The main process of calculating the entropy-weight
refrigerated condition. water quality index is as follows:
  Firstly, the initial matrix X is constructed with
xij  xij min
yij ¼     ð1Þ sample number and hydrochemical parameters, and
xij max  xij min then the judgment matrix Y is obtained by normaliza-
  tion. In matrix Y, yij is calculated from Eq. (1), and
1 þ yij (xij)min and (xij)max represent the minimum and
pij ¼ 1 þ Pm   ð2Þ
i¼1 1 þ yij maximum values of the same water chemistry param-
eters for all samples in matrix X, respectively. Then,
1 X m
information entropy (ej), entropy weight (wj), and
ej ¼  Pij ln Pij ð3Þ
ln m i¼1 quality assessment quantity (qi) are calculated from
Eqs. (2)–(5), where Cj is the concentration (mg/L) of
1  ej parameter j and sj is the permissible limit value (mg/L)
wj ¼ Pn   ð4Þ
j¼i 1  ej of parameter j. Finally, EWQI is calculated using
Eq. (6) (Ji et al., 2020; Liu, 2020b).
Cj When EWQI \ 25, groundwater quality is excel-
qj ¼  100 ð5Þ
Sj lent; when 25 \ EWQI \ 50, groundwater quality is
good; when 50 \ EWQI \ 100, groundwater quality
X
m
is moderate; when 100 \ EWQI \ 150, groundwater
EWQI ¼ wj qj ð6Þ
i¼1
quality is poor; when EWQI [ 150, water quality
grade is very poor.
TDS and pH were measured directly at the
sampling point using a portable instrument (HACH, Health risk assessment
H40D), major cations (potassium, sodium, calcium,
magnesium), metasilicate and total hardness were The Health Risk Assessment Method (HRA) is a
determined by inductively coupled plasma emission quantitative method for assessing the relationship
spectroscopy (ICP-AES, optima 7000DV), sulfate, between harmful substances in groundwater and
chloride, and nitrate ions were determined by ion human health. The assessment model includes hazard
chromatography, and bicarbonate ions were deter- identification, dose-effect analysis, exposure assess-
mined by titration (ICS-600). Calculating the ion ment and risk characterization (Adimalla & Qian,
equilibrium error (IBE), each sample was found to 2020; Wu et al., 2021). In this study, the health risks
have an acceptable range of error (approximately associated with ingestion via drinking and dermal
10%) (Ion et al., 2019; Zhang et al., 2018). contact were calculated for adult males, females, and
children based on a model provided by the U.S.

123

Environmental Protection Agency (USEPA) as
follows:
C  IR  EF  ED
CDIOral ¼ ð7Þ
ABW  AET
TC  C  SA  Ki  EV  EF  ED  CF
CDIDermal ¼
BW  AET
ð8Þ
CDIOral þ CDIDernal
HI ¼ ð9Þ
DRf
CDI is the estimated chronic daily intake of
contaminants, including the oral drinking dose CDIOral
and the dermal absorbed dose CDIDermal, in mg/
(kgdays). C is the concentration of nitrate in ground-
water (mg/L); IR is the drinking water intake rate in
L/day: 1.32 for children and 2.62 for adults. ED and
EF are the exposure duration (years) and exposure
frequency (days/year), respectively. The ED value is
45 for males and females and 12 for children, and EF is
365. ABW stands for average body weight (kg), and
the recommended weights are 65 kg for men, 55 kg
for women, and 28 kg for children; AET stands for
average exposure time, with values of 23,360 days,
24,455 days, and 4380 days for men, women and
children, respectively.
TC stands for duration of exposure, 0.4 h/day. SA
stands for skin surface area, with values of 16,600 cm2
for adults and 12,000 cm2 for children. Ki is the skin
absorption parameter (cm/h: 0.001 cm/h); EV is the
frequency of bathing (times/day: considered as once a
day); and the conversion factor (CF) is designated as
0.001. DRf is the reference dose, and its value for
NO3- is 1.6 mg/kg/day according to the USEPA. The
sum of CDIOral and CDIDermal is the total risk,
expressed by HI; HI \ 1 indicates an acceptable risk;
otherwise, the risk exceeds an acceptable level (Adi-
malla & Qian, 2021; Liu et al., 2020b).
Results and discussion
General hydrochemistry of groundwater
Statistical analysis of hydrochemical data can provide
preliminary understanding of the typical characteris-
tics of water chemistry in the study area. According to
the general standard (Gao, 2019c), the pH standard for
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Environ Geochem Health
drinking water is 6.5–8.5, and the groundwater in the
study area was weakly alkaline, with a maximum pH
value of 8.7. As shown in Table 1, there were 4 samples
with alkalinity levels slightly above the standard,
which does not affect human health. When the total
dissolved solids (TDS) \ 1000 mg/L, groundwater is
called fresh water; when the total hardness (TH) \
450 mg/L, groundwater is called soft water; water
with low TDS and low TH is less not suitable for human
consumption (Barzegari et al., 2017). The TDS of some
samples in the study area exceeded the standard, with a
maximum value of 1907.44 mg/L and an exceedance
rate of 12%. The maximum value of total hardness was
829.49 mg/L, and the percentage of exceedance was
11%. According to the average value, the main anions
and cations in the groundwater in this region are Na?
and HCO3-, and anion abundance followed the order
HCO3- [ SO42- [ Cl- [ NO3-, while the cation
abundance followed the order Na? [ Ca2? [ Mg2?-
[ K?. The standard value of NO3- concentration is
50 mg/L and the detection limit of the instrument is
0.01 mg/L. NO3- was not detected in 5 of the 89
samples in the NNLC, and the exceedance rate was
27%. The samples showed significant nitrate contam-
ination with a large variation in values among samples.
The coefficient of variation (CV) is the standard
deviation divided by the mean of the overall sample,
which reflects the degree of stability of an indicator
(Abdul-Wahab et al., 2020). As shown in Table 1, the
data are stable when CV is \ 40%, except for pH; the
only other indicator that met this criterion was
HCO3-, which indirectly indicates that the source of
HCO3- is widespread and evenly distributed in the
study area. In addition, the CV for TDS, TH, and Ca2?
ranged from 50 to 70%, indicating that the levels of
these indicators may vary in different regions. The CV
for Na?, K?, SO42-, Cl-, NO3-, ranged from 100 to
120%. These large values may be attributable to point
and diffused pollution from industrial and agricultural
activities.
Cluster analysis and regional classification
analysis
CA reveals complex interrelationships between water
samples or indicators by extracting important infor-
mation hidden in the raw data population, making it
easier to summarize the main factors influencing water
chemistry characteristics from a wide range of factors
Environ Geochem Health

Table 1 Statistical Parameters Units Minimum Maximum Mean SD CV (%)

summary the main chemical
properties of groundwater pH – 7.3 8.7 7.81 0.31 3.95
of the NNLC
TDS mg/L 157.97 1907.44 561.26 379.3 67.58
TH mg/L 96.08 829.49 285.68 164.41 57.55
Ca2? mg/L 10.77 185.24 71.88 39.75 55.29
Mg2? mg/L 0.52 131.82 25.55 24.97 97.74
?
Na mg/L 2.36 413.33 78.21 92.33 118.06
K? mg/L 0.52 9.23 1.44 1.44 99.52
HCO3- mg/L 90.97 441.84 181.81 72.86 40.08
SO42- mg/L 6.57 789.35 155.02 168.71 108.83
Cl- mg/L 5.58 399.81 80.82 79.57 98.46
NO3- mg/L 0 171.09 35.21 36.97 105.01
CV coefficient of variation, SiO2 mg/L 1.6 37.73 23.61 7.71 32.66
SD standard deviation

and indicators, and to interpret the main factors
quantitatively (Zhang et al., 2020a). In CA, neighbor-
ing samples have similar hydrochemical characteris-
tics, and the correlation features are projected onto the
groundwater sampling point distribution map. Most of
the sampling sites were found to have strong correla-
tion in both CA and spatial distribution. Moreover,
coupled with the relatively complex human activities
in the study area, strong regional variation was
observed in groundwater in the study area (Madhav
et al., 2020). As shown in Fig. 2, the sampling points
were grouped according to the order of spatial
distribution and hierarchical CA and projected on the
hydrogeologic map of the NNLC region. The three
groups of water samples exhibited extremely distinct
regional differences and correlated well with the
geomorphological and hydrogeological features.
Accordingly, three regions could be set for the groups
of samples: the Yellow River Alluvial Plain (Group I,
indicated in yellow), which has low topography and
shallow groundwater depth; the Taiyi Mountains
Apron Plain (Group II, indicated in red) north of the
Nansi Lake, which has low topography and deep
groundwater depth; the Taiyi Mountains Front Low
Hills and its Front Margin (Group III, indicated in
blue) in the eastern part of the NNLC, which has high
topography.
grouped samples were projected onto the piper
triangles. To clarify regional differences in the chem-
ical characteristics of groundwater in the study area,
the samples were classified into groups I, II, and III of
the cluster analysis. In general, the water chemistry
types in the study area are complex, with large
variations in anion or cation, even within a single
group. The anions in Group I are stable and correspond
to the SO4–Cl type, with no predominant anion. In
contrast, the cations are highly variable, with approx-
imately 40% corresponding to the Na–K type, and are
concentrated near the southern boundary of the
Yellow River Alluvial Plain; the dominant cation is
Na?. The cations in the water samples of Group II are
stable and correspond to the Ca-Mg type. The anions
exhibit large variations, with 30% corresponding to
the SO4-Cl type, and are distributed near the east–west
boundary of the Taiyi Mountains Apron Plain. On the
whole, approximately 70% of the samples correspond
to the HCO3–CaMg type. The specific gravity of
anions and cations in Group III was relatively stable,
with the cations mostly located in region A and Ca2?
as the dominant ions; the anion is basically located in
the B region, which is the non-dominant region.
Specific gravity did not significantly vary between the
three major anions, and Cl- content was slightly
lower.

Hydrochemical types Natural processes controlling the formation

of groundwater chemistry
The Piper diagram is a practical method for easy
classification of water chemistry types for multiple Gibbs diagram can be used to analyze the main natural
samples (Gao, 2019b). As shown in Fig. 3, the factors influencing the formation of the chemical

123

Fig. 2 Hydrogeological maps of the NNLC and clustering analysis results
components of groundwater (Li et al., 2016a). The
three sample groups were plotted in a Gibbs diagram,
as shown in Fig. 4. Firstly, Na?/(Na? ? Ca2?) was
found to be significantly higher than Cl-/(Cl--
? HCO3-) in Group I and II, and Na?/(Na? ? Ca2?)
was extremely high in some water samples (Fig. 4a),
exceeding the analytical range delineated by Gibbs’s
diagram. This indicates the potential effects of
anthropogenic factors, evaporation, and silicate dis-
solution to increase Na?. These samples were mostly
located in the southwestern and central parts of the
study area. In addition, without considering the
anthropogenic influence of Na ? , the entire study
area is predominantly controlled by rock-water inter-
action. Samples in Group I are more controlled by
evaporation than those in the other two groups. This is
attributable to the flat topography, shallow depth of
groundwater, and poor hydrodynamic conditions of
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Environ Geochem Health
the Yellow River alluvial plain. In the NNLC,
evaporation increases gradually from northeast to
southwest (Liu et al., 2021).
Ion ratio of dissolved minerals
The dissolution of different minerals produces differ-
ent types or ratios of ions, and this process can be
calculated quantitatively (Karunanidhi, 2020; Zhu
et al., 2017). Ionic ratios can help analyze the effects
of the dissolution of different minerals on groundwater
chemistry. In Fig. 5a, natural causes are further
divided on the basis of the Gibbs plots (Yan et al.,
2020). Specifically, Group I and a small number of
Group II are controlled by evaporation. Group II and
Group III are mainly affected by the dissolution of
silicate and carbonate, with Group II being affected
more strongly. An Na?/Cl- ratio of approximately 1
Environ Geochem Health

Fig. 3 Piper diagram representing the chemistry of groundwater

Fig. 4 Gibbs plots of groundwater samples in the NNLC

123

indicates dissolved rock salt, which occurs as per
Eq. (10), as the theoretical source of Na? and Cl-:
NaCl ! Naþ þ Cl ð10Þ
As shown in Fig. 5b, the equivalent concentrations
of Na? and Cl- in Group I were mostly higher than
5 meq/L, with extremely large and irregular degrees of
variation, mainly attributable to Na? overflow; this
indicates that Na? has other major sources apart from
rock weathering (Amiri et al., 2020). Na? and Cl-
equivalent concentrations in Groups II and III were
Fig. 5 Scatter plots of major ions
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Environ Geochem Health
mostly lower than 5 meq/L and generally near the 1:1
line, mainly controlled by rock salt dissolution, but
Na? was high in Group II and Cl- was high in Group
III, which correspond with the different water chem-
istry types of the two groups in Fig. 3. If the
groundwater hydrochemistry is mainly controlled by
the dissolution of calcite (CaCO3), dolomite
(CaMg(CO3)2), and gypsum or anhydrite (CaSO4),
then c(Ca2? ? Mg2?)/c(HCO3- ? SO42-) should be
distributed near the 1:1 line in Fig. 5c (Ion et al.,
2019). The dissolved equivalent concentration is
Environ Geochem Health
approximately 2.5 to 12.5 meq/L. The pattern of anion
and cation distribution along the 1:1 line in Fig. 5c is
reversed from that in Fig. 5b.
To further clarify the type of dissolved carbonate
rock, the c(Ca2? ? Mg2?)/c(HCO3-) plot (Mandal
et al., 2021) was generated, as shown in Fig. 5d. If
only calcite and dolomite dissolution occurred, then
the meq concentration ratio of Ca2? ? Mg2? and
HCO3- should be 1:1 as per Eqs. (11) and (12)
(Sohrabi et al., 2020):
CaCO3 þ CO2 þ H2 O ! Ca2þ þ 2HCO
3 ð11Þ
CaMgðCO3 Þ2 þ 2CO2 þ 2H2 O
! Mg2þ þ Ca2þ þ 4HCO 3 ð12Þ
Figure 5a shows that Groups I and II are affected by
the dissolution of silicate minerals to a considerable
extent. The stability diagram, which has been pro-
posed to analyze silicate dissolution by (Drever, 1997;
Trady, 1971), was drawn (Fig. 5e). In this study, the
content of K? was low, only considering the conver-
sion of albite to kaolin as per Eq. (13):
2NaAlSi3 O8 þ 2CO2 þ 11H2 O
! Al2 Si2 O5 ðOHÞ4 þ 4H4 SiO4 þ 2Naþ þ 2HCO
3 under normal circumstances less gypsum minerals are
ð13Þ
Gypsum or anhydrite is the main sources of
groundwater SO42- in nature. The piper diagram
indicates the occurrence of gypsum dissolution in
Groups I and III to a certain extent. Gypsum dissolves
to produce equal amounts of Ca2? and SO42- as per
Eq. (14) (Liu et al., 2020b):
CaSO4 ! Ca2þ þ SO2
4 ð14Þ
In the c(Ca2? ? Mg2?)/c(HCO3-) plot in Fig. 5d,
a large number of Group II samples are distributed
around the y = x line. Combined with the Piper
diagram, the specific gravity of Mg is between 20
and 50, and dolomite dissolved in the groundwater of
Group II accounted for a large proportion. Group III
samples presented an abnormal distribution. The
concentration of HCO3- was maintained at approxi-
mately 2 meq/L, but the concentration of Ca2?-
? Mg2? gradually increased from 2 to 8 meq/L. In
the c(Ca2?)/c(SO42-) plot in Fig. 5f, Group III
samples are distributed close to the y = x ? 2 line;
2 meq/L of c(Ca2? ? Mg2?)/c(HCO3-) could be
determined to be derived from calcite. A small amount
of calcite is generally dissolved in Group 2, suggesting
that it is mainly affected by the dissolution of gypsum.
Silicate degradation is incongruent, and this process
cannot be quantified by a simple scatter plot; the
boundaries in the Fig. 5e distinguishes the areas where
different minerals reach stability (Vaiphei et al.,
2020). The stable mineral in Groups I and II is albite,
and that in Group III is kaolinite. Albite is unstable at
room temperature, indicating that the conversion of
albite in Groups I and II has reached saturation, further
suggesting its higher contribution to the chemical
composition of groundwater.
Group I samples exhibited an irregular and highly
variable distribution (Fig. 5b–f), which will be
inferred from the unstable and high concentration of
Na? and SO42-, as well as evaporation and silicate
degradation. The sources of Na? and SO42- in Group I
samples could be inferred from the c(Na?)/c(SO42-)
plot in Fig. 5g; the equivalent concentrations of Na?
and SO42-ranged from 5 to 20 meq/L. Sample distri-
bution along the y = x line is symmetrical, but still
varies significantly. The Mirabilite is a naturally
occurring mineral that produces the same amounts
(meq) of Na? and SO42- on dissolution. However,
less abundant in sediments. Moreover, the study area
does not include any Mirabilite mine. Na? and SO42-
may be strongly affected by human activities, which is
discussed in a later section.
Cation exchange
Cation exchange is a common chemical reaction
between groundwater and water-bearing rock forma-
tions. When cation exchange occurs forward Na? and
K? in groundwater replace Ca2? and Mg2? in
minerals (Zhang et al., 2020a). The scatter plot
between the ionic charge of (Ca2? ? Mg2?) -
(HCO3- ? SO42-) and Na? ? K? - Cl- was used
to verify whether cation exchange had a significant
effect on the chemical composition of groundwater.
This conjecture is verified when its ratio is approxi-
mately - 1. As shown in Fig. 5h, all water samples in
the study area are located around the - 1:1 line,
indicating that cation exchange has a significant effect
on the development of groundwater chemical compo-
sition in the NNLC. The chlor-alkali index (CAI) can
further indicate the direction along which cation
exchange occurs (Li et al., 2016a), with two
123

indicators: CAI-I for (Cl- - Na? - K?)/Cl- and
CAI-II for (Cl- - Na? - K?)/(HCO3- ? SO42--
? Cl- ? NO3-). When CAI [ 0, the cation
exchange action is forward; when CAI \ 0, the cation
exchange action is reverse. As shown in Fig. 5i,
CAI \ 0 for most samples in Groups I and II, Ca2?
and Mg2? in groundwater replaced Na? and K? in
minerals. Both forward and reverse reactions occurred
in Group III, but the intensity of the reactions was
weaker.
Effects of human activities
In the above analysis, some of the ions such as SO42-,
Ca2?, and Na? showed characteristics clearly beyond
the control of natural causes, and the groundwater in
the NNLC may be strongly influenced by human
activities. In contrast to natural causes, human activ-
ities release agricultural fertilizers, industrial wastew-
ater, and domestic sewage into groundwater, resulting
in the input of large amounts of SO42-, Cl-, and
NO3-. Among naturally produced ions, NO3- is
generally produced in small amounts by nitrification,
and several studies have shown that higher concen-
trations of NO3- in groundwater are generally asso-
ciated with agricultural activities (Wu & Sun, 2015).
The end-element diagram of (NO3-/Na?) and (Cl-/
Na?) is shown in Fig. 6a as an indication of the impact
of agricultural activities on groundwater (Kou et al.,
2019). Figure 6a presents the effects of agricultural
activities on the three groups of groundwater: III [
II [ I. However, this diagram only indicates the
effects of agricultural activities with nitrate applica-
tion and could not account for the abnormal excesses
of SO42-, Ca2?, and Na? in the NNLC, especially in
Group I. Therefore, the improved ratio diagram of
(SO42-/Ca2?) to (NO3-/Na?) was adopted to com-
prehensively represent the pollution of groundwater
by two major types of pollution, i.e., sulfur-containing
fertilizers and industrial wastewater, nitrate-contain-
ing fertilizers and domestic wastewater (Liu et al.,
2020b).
As shown in Fig. 6b, the two pollution types are
polarized in Group I and Group III. Group I is mainly
polluted by sulfate from sulfur-containing fertilizers
and industrial wastewater. Hydrogeologically, the
alluvial plain of the Yellow River is flat, with poor
hydrodynamic conditions, high salinization, and high
TDS and TH in groundwater. In combination with the
123
Environ Geochem Health
socio-economic situation, Jinxiang County in this
region is famous as a garlic producing area in China
(Geng et al., 2013). Sulfur-containing (e.g., gypsum)
fertilizers are often used in garlic cultivation. On one
hand, gypsum can be added to biochar to improve the
salinity and alkalinity of the visible soil (Zhang et al.,
2020b). On the other hand, the application of gypsum
fertilizer can improve the nutritional value of garlic
based on the ability of garlic bulbs to concentrate
sulfur and selenium (Sohrabi et al., 2020). Therefore,
we can analyze the order in which agricultural
activities in this region affect groundwater. Farmers
apply sulfur-containing (e.g. gypsum) fertilizers,
which on the one hand produce de-dolomitization
(Liu et al., 2020c), depositing CaCO3 and lowering
TDS and TH in groundwater. On the other hand, a
cation exchange reaction occurs and excess Ca2? and
Mg2? displaces Na? and K? in shallow aquifer
minerals, which collectively results in a significant
increase in Na? and SO42- concentrations. In addi-
tion, Group III samples and part of Group II samples
were contaminated with nitrate, and the distribution
characteristics of the nitrate are analyzed in the
following discussion.
Factors influencing the development of the ground-
water hydrochemistry of the three groups can be
summarized as follows: (1) Group I distributed in the
Yellow River Alluvial Plain. Due to the combined
effects of evaporation, albite dissolution, cation
exchange, and sulfate pollution caused by human
activities, the groundwater chemistry characteristics
are complex and rare. (2) Group II distributed in the
Taiyi Mountains Apron Plain. The hydrochemistry is
attributable to typical dolomite dissolution, with a
small contribution from albite dissolution and cation
exchange. Group III distributed in the Taiyi Mountains
Front Low Hills and its Front Margin. Based on the
dissolution of a small amount of calcite, the ground-
water chemistry characteristics are controlled by the
dissolution of gypsum minerals, while nitrate pollu-
tion and other causes have low impact. In the analysis
process, except for a small number of Group II
samples mixed with Group III samples, differences in
the groundwater chemistry characteristics and causes
of the three groups were significant and efficacious.
Therefore, the integration of CA and spatial distribu-
tion exhibited excellent performance for classification,
which is of significance for further research and
application.
Environ Geochem Health
Fig. 6 Plots of a Cl-/Na? versus NO3-/Na? and b NO3-/Na? versus SO42-/Ca2?
Water quality assessment
The Entropy-Weight Water Quality Index (EWQI) is
an integrated, comprehensive, and stable method for
evaluating water quality (Amiri et al., 2020). The
calculated EWQI results are integrated and shown in
Fig. 7a, and the groundwater quality was found to be
generally good and moderate. However, 7 samples
showed poor water quality and 4 samples showed very
poor water quality, totaling 11 samples (12.36%), of
which 10 belonged to Group I. Group 1 mostly
accounted for samples with excellent water quality,
but the difference in water quality characteristics
within the groups was significant. According to the
average value, the overall water quality in the three
groups is excellent and followed the order III [ II [ I.
The spatial distribution map can clearly present the
distribution and changes of water quality (Vaiphei
et al., 2020). Figure 7b shows that the overall water
quality in the study area gradually deteriorated from
northeast to southwest. The water quality is poor and
very poor in the Yellow River Alluvial Plain where
Group I was concentrated, mainly in and around
Jinxiang County and Yutai County, accounting for
approximately 20% of the total area. Moderate water
quality accounted for approximately 40–50% of the
area, indicating that this part in the NNLC is at risk of
deteriorating to poor quality water. The spatial distri-
bution of water quality is similar to the depth
distribution of the groundwater table (Fig. 2), with
poorer water quality and higher SO42- content in areas
of shallow groundwater depth, which is attributable to
stronger evaporation and the application of sulfur-
containing fertilizers. Considering both the bar graph
and spatial distribution map, the groundwater quality
widely varies, with significant regional differences.
Most samples and grade areas are dominated by good
and medium quality water. Compared with good
quality groundwater, SO42- is prominently higher in
moderate quality water. Industrial and agricultural
sulfate-discharging activities should be reduced to
prevent further deterioration of groundwater quality.
Spatial distribution of nitrates and health risk
assessment
The above analysis shows that nitrate mainly origi-
nates from human activities. However, it had less
weight in the water quality evaluation because of its
low concentration and low pollution standards. Con-
sequently, its distribution characteristics and degree of
pollution could not be visualized. Hence, nitrate
concentration was projected onto the map of the study
area, and the spatial distribution of nitrate concentra-
tion was determined suing ArcGIS software based on
the inverse distance weighting method of interpolation
(Fig. 8). According to the International Health Orga-
nization (WHO), a nitrate concentration of 50 mg/L is
considered to be pollution. As shown in Fig. 8, the
area of excess nitrate concentration accounted for
approximately 30% of the total area. Areas with wide
extent and seriously exceeding values of nitrate are
mostly located in the hilly areas of the Midwest and
East, which are polluted by agricultural fertilization.
123

Fig. 7 Statistical bar graph (a) and spatial distribution (b) of EWQI in the NNLC
Areas with small extent and slightly exceeding values
are distributed in urban areas close to counties and
cities, which are polluted by domestic sewage dis-
charges (Wang et al., 2020).
The concentration of nitrate is closely related to
agricultural activities, and nitrate pollution of ground-
water caused by agricultural activities has gradually
become a global environmental problem (Wu et al.,
2021). Excessive intake of nitrates in humans causes
methemoglobinemia and increases the risk of a
Fig. 8 Spatial distribution of nitrate concentration
123
Environ Geochem Health
number of diseases (Vlachou et al., 2020). Human
health risk assessment is an effective method for
determining the extent to which pollution poses a risk
to human health, and was originally proposed by the
USEPA. The risk assessment value (HI) of nitrate for
human health was calculated on the basis of the model
given by the USEPA and parameters modified from
previous studies. The results are shown in Fig. 9. Risk
levels were found to vary for different populations:
children [ female [ male. The number of samples
with HI [ 1 in children, male, and female were 42, 29,
and 37, respectively. Liu et al. (2020c) subdivided risk
levels, with HI \ 1 for no risk, 1 \ HI \ 2 for low
risk, 2 \ HI \ 3 for moderate risk, 3 \ HI \ 4 for
high risk, and HI [ 4 for extreme risk. Children were
at higher risk, with six samples reaching high and
extreme risk. Only one and two samples were above
medium risk for both males and females. Compared
with adults, children are at a slightly higher risk, with
six samples reaching high and extreme risk. The box
range represents most aggregate levels, with no risk
for males and females overall, no or low risk for
children overall, indicating that direct consumption of
groundwater can have health effects on children. HI
and nitrate exhibited the same spatial distribution
characteristics. As suggested by the results presented
in Fig. 9, the effects of nitrate contamination should be
considered when exploiting hilly and surrounding
urban groundwater for drinking water, and targeted
Environ Geochem Health
Fig. 9 Results of health risk evaluation in different populations
nitrate removal measures should be implemented
when providing drinking water to children.
Conclusion
(1) Groundwater in NNLC is generally fresh and
soft water, with Na? and Ca2? as the major
anions and HCO3- as the major anions. CA and
spatial distribution were integrated to divide the
groundwater samples into three groups, which
corresponded well to the geomorphological
units of the study area. Groups I, II, and III
correspond to the Yellow River alluvial plain,
the Taiyi Mountains apron plain, and the Taiyi
Mountains front low hills and front margin,
respectively. According to the analysis of
groundwater chemical characteristics and
causes, the classification performance is excel-
lent, and it is of significance to further research
and application.
(2) According to the Piper diagram, the hydro-
chemical types of groundwater in Groups I and
II are Na-SO4Cl and CaMg-HCO3, respec-
tively, while that in Group III is more concen-
trated, mostly corresponding to Ca-HCO3. The
Gibbs diagram showed that the natural causes
are mostly water–rock interactions. The effect
of evaporation gradually weakened from Group
III to II to I. Multiple scatter plots showed that
the main dissolved minerals in the study area are
calcite, dolomite, gypsum, and albite.
Considering mineral dissolution, cation
exchange, and human activities, the three
groups of groundwater are significantly affected
by the following factors: evaporation, albite
dissolution, cation exchange, and sulfate pollu-
tion for Group I; dolomite dissolution, albite
dissolution, and cation exchange for Group II;
gypsum dissolution, and calcite and nitrate
pollution for Group III.
(3) According to EWQI for evaluating the water
quality of the study area, the proportion of
samples exceeding the standard was \ 15%, the
water quality was good and medium in most
samples, and the overall water quality was
excellent, following the order III [ II [ I. From
the spatial distribution of nitrate concentrations,
high concentrations of nitrate can be observed to
be mainly distributed in hilly areas and around
urban areas, with approximately 20% of the
total area exceeding the standard. In terms of the
target populations, the health risk can be ordered
as follows: children [ female [ male. In most
aggregate levels, adults were at no risk, and
children were at no risk and low risk. The impact
of nitrate pollution should be considered when
exploiting groundwater for drinking water in
hilly areas and around cities.
Acknowledgements We thank the anonymous reviewers and
Editor for their useful comments, which helped improve the
manuscript.
Author contribution ZG contributed to formal analysis and
writing—original draft. CH contributed to formal analysis,
software, and methodology. SY was involved in formal analysis,
software, and methodology. JL contributed to
conceptualization, writing—original draft, and writing—
review and editing. YP contributed to funding acquisition and
resources. CL contributed to investigation, resources, and
funding acquisition.
Funding This research was funded by National Natural
Science Foundation of China (No. 41772257; 41472216), the
Research Project of Shandong Province Bureau of Geology and
Mineral Resources (No. KY2018003; KY201933), the
Shandong Provincial Geological Environment Exploration
Project (2016) No.3 and the 68th batch of general projects of
the China Postdoctoral Science Foundation (2020M682207).
Declarations
Conflict of interest The authors declare that they have no
conflict of interest.
123

Ethical approval Ethics approval was not required for this
research.
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