Article

Comprehensive Hydrochemical Analysis, Controlling

Mechanisms, and Water Quality Assessment of Surface
and Groundwater in a Typical Intensive Agricultural Area,
Northern China
Zongjun Gao 1 , Tingting Huang 1 , Jinkai Chen 1,2 , Hong Tian 1, *, Menghan Tan 1 , Yiru Niu 1 and Kexin Lou 1

1 College of Earth Science and Engineering, Shandong University of Science and Technology,
Qingdao 266590, China; [email protected] (Z.G.); [email protected] (T.H.); [email protected] (J.C.);
[email protected] (M.T.); [email protected] (Y.N.); [email protected] (K.L.)
2 No. 3 Exploration Institute of Geology and Mineral Resources, Yantai 264000, China
* Correspondence: [email protected]

Abstract: Groundwater is a significant source of water, and evaluating its hydrochemical

attributes, quality, and associated health risks holds paramount importance in guaranteeing
safe water access for the population and fostering sustainable socio-economic progress.
Situated within a semi-arid region, the Dianbu area (DBA) features numerous greenhouses
interspersed amongst open farmlands. An examination revealed a discernible decline in
the overall water chemistry environment in this area. This study extensively examined the
fundamental water chemistry characteristics of groundwater and surface water samples
through a statistical analysis, Piper’s trilinear diagram, ion ratios, and other analytical
methods. The assessment of irrigation water quality was conducted using the entropy
weight water quality index (EWQI), sodium adsorption ratio (SAR), percentage of solu-
ble sodium (Na%), among other relevant indicators. The findings demonstrate multiple
key aspects: 1. Water cations are chiefly composed of Ca2+ and Na+ , while groundwater
anions are notably NO3 − and SO4 2− dominant, defining the water type as NO3 -SO4 -Ca.
Academic Editor: Fernando António Conversely, surface water primarily displays HCO3 − and SO4 2− anions, aligning it with
Leal Pacheco an HCO3 -SO4 -Ca water type. 2. The extensive agricultural activities in the region, coupled
Received: 28 November 2024 with the excessive utilization of pesticides, chemical fertilizers, as well as the discharge of
Revised: 15 January 2025 domestic sewage, contribute to heightened NO3 − concentrations in groundwater. 3. The wa-
Accepted: 17 January 2025
ter quality assessments indicate that approximately 53% of agricultural water quality meets
Published: 19 January 2025
irrigation standards based on EWQI, with SAR results suggesting around 65.52% suitability
Citation: Gao, Z.; Huang, T.; Chen, J.;
for irrigation and Na% findings indicating approximately 55.88% viability for this purpose.
Tian, H.; Tan, M.; Niu, Y.; Lou, K.
Proper water selection tailored to specific conditions is advised to mitigate potential soil
Comprehensive Hydrochemical
Analysis, Controlling Mechanisms,
salinization risks associated with long-term irrational irrigation practices.
and Water Quality Assessment of
Surface and Groundwater in a Typical Keywords: typical agricultural area; groundwater; hydrochemical characteristics; water
Intensive Agricultural Area, Northern quality evaluation
China. Water 2025, 17, 276. https://
doi.org/10.3390/w17020276

Copyright: © 2025 by the authors.

Licensee MDPI, Basel, Switzerland. 1. Introduction
This article is an open access article
Groundwater is of utmost importance in the daily routines of inhabitants and promot-
distributed under the terms and
ing agricultural progress [1]. According to Siebert et al. [2], global consumptive groundwa-
conditions of the Creative Commons
Attribution (CC BY) license
ter use for irrigation totals 545 km3 per year, representing 43% of the total consumptive
(https://creativecommons.org/ irrigation water use of 1277 km3 per year. China stands out as one of the largest countries in
licenses/by/4.0/). terms of groundwater irrigated area, with 19 million hectares under irrigation. Meanwhile,

Water 2025, 17, 276 https://doi.org/10.3390/w17020276

Water 2025, 17, 276 2 of 17

particularly in arid and semi-arid regions, where surface water is scarce [3], groundwater
plays a vital role in supporting rural, industrial, agricultural, and urban water needs [4].
However, numerous regional aquifers worldwide, particularly in intensively cultivated
areas, are presently experiencing severe anthropogenic contamination resulting from the
rapid modernization of agriculture, urbanization, and industrial development [5,6]. There-
fore, conducting hydrochemical analyses and water quality assessments in agricultural
regions is important for the conservation of water resources and the promotion of sustain-
able development in farming areas [7,8].
Shandong’s Laixi Dianbu (DBA), situated in the semi-arid region of the Jiaodong
Peninsula, stands out as a typical agricultural area. Therefore, investigating the hydrochem-
ical characteristics and water quality status of groundwater in this region holds significant
practical importance. Zhang et al. [9] conducted an evaluation of the hydrochemical char-
acteristics, ion sources, and water quality in the arid regions using correlation analysis,
Piper trilinear diagram, Gibbs diagram, and ion ratios. Nadjai et al. [10] evaluated the
groundwater quality for irrigation purposes in the semi-arid Middle Cheliff region using
methods such as SAR and Na%. Therefore, this study utilizes DBA hydrochemical data
to delineate the hydrochemical characteristics of DBA surface and groundwater. The as-
sessment encompasses both irrigation water quality of surface and groundwater, offering
scientific groundwork and a reference for the sustainable development of groundwater
resources in the region.

2. Materials and Methods

2.1. Study Area
The study site is situated in the DBA of Laixi City, Shandong Province (Figure 1).
Laixi City lies at the heart of the Shandong Peninsula, characterized by a topography where
northern areas are elevated, while southern regions are lower, featuring low hills to the
north, gradually sloping plains in the central area, and basin-like depressions in the south.
Laixi City is situated within North China’s warm temperate monsoon continental climate,
influenced by geographic conditions and monsoon winds. This results in significant inter-
annual variations in precipitation with uneven spatial and temporal distribution. The
area primarily falls within the Dagu River system, with the river flowing southwards
through the central part of the region. Groundwater primarily resides in the pore spaces
of sand layers, weathered fissures in bedrock, and tectonic fissures. Groundwater in the
DBA predominantly comprises pore water from loose rock and pore fissure water from
clastic rock [11]. The upper part of the aquifer consists of a loose sand layer, while the
lower part comprises sedimentary and metamorphic rock. Groundwater recharge primarily
stems from atmospheric precipitation infiltration, with evaporation and artificial pumping
representing the main methods of groundwater discharge. Groundwater movement aligns
with the topographic slope and surface water system, gently sloping from north to south.
Water2025,
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x FOR PEER REVIEW 3 of 17
3 of 17

Figure 1. Schematic map of the DBA and location of sampling sites.

Figure 1. Schematic map of the DBA and location of sampling sites.
2.2. Sampling and Measurement
2.2. Sampling and Measurement
Considering the local farming practices, this research collected 34 water samples in
Considering
November, whichthe localthe
marks farming practices,
dry season this1).
(Figure research collected
Of these, 34 water samples
29 groundwater samplingin
November,
points were which
locatedmarks
around thevegetable
dry season (Figure 1). and
greenhouses Of these, 29 groundwater
cultivated land, drawingsampling
from
points were located around vegetable greenhouses and cultivated land,
shallow groundwater through mechanized wells with an average depth of 7 m. Addition- drawing from
shallow
ally, theregroundwater through
were five surface mechanized wells
water-sampling with
points, an average
specifically depth
from theof 7 m. River
Dagu Addition-
and
ally, there were five surface water-sampling points, specifically from the Dagu
drainage canal water. Table 1 provides details on the testing methods for each indicator. River and
drainage canal water. Table 1 provides details on the testing methods for each indicator.
Table 1. Test methods and detection limit of groundwater samples.
Table 1. Test methods and detection limit of groundwater samples.
Testing Indicators Detection Methods/Instruments Detection Iimit/(5 mg·L−1 ) −1
Testing Indicators Detection Methods/Instruments Detection Iimit/(5 mg·L )
Cl− Cl− Volumetric silver nitrate
Volumetric silvermethod
nitrate method 0.050.05
Ca2+ , Mg2+2+ , TH (CaCO 3 ) Disodium EDTA titration method 0.05
Ca ,+Mg2++, TH (CaCO 3) Disodium EDTA titration method 0.05
K , Na+ Flame atomic absorption spectrophotometry 0.05
K , Na + Flame atomic absorption method
spectrophotometry 0.050.05
SO4 2− Barium sulfate turbidimetric
NO3 −SO 42− Barium sulfate turbidimetric
Ultraviolet spectrophotometric method method 0.200.05
pH NO3 − Ultraviolet
Glass spectrophotometric
electrode method method 0.010.20
TDS pH American HACH hash Glass electrode
portable method
pH meter HQ40D 0.010.01
TDS American HACH hash portable pH meter HQ40D 0.01
2.3. Methods
2.3. Methods
The hydrochemical attributes and genesis mechanisms of surface and groundwater in
The hydrochemical attributes and genesis mechanisms of surface and groundwater
the DBA were examined through conventional techniques, including Piper’s plot, Gibbs
in the DBA were examined through conventional techniques, including Piper’s plot, Gibbs
plot, correlation analysis, ion ratio analysis, etc. Additionally, the water quality assessment
plot, correlation analysis, ion ratio analysis, etc. Additionally, the water quality assess-
in the area employed parameters such as EWQI, SAR, and Na%. By utilizing ArcGIS (10.8)
ment in the area employed parameters such as EWQI, SAR, and Na%. By utilizing ArcGIS
software, the spatial arrangement of sampling sites within the study area was delineated to
(10.8) software, the spatial arrangement of sampling sites within the study area was de-
elucidate the primary chemical components and water quality of both groundwater and
lineated to elucidate the primary chemical components and water quality of both ground-
surface water in this locale.
water and surface water in this locale.
2.3.1. The Entropy Water Quality Index (EWQI)
2.3.1. The Entropy Water Quality Index (EWQI)
The entropy weighting method for assessing water quality involves computing sub-
indexThe entropy
data, weighting
assigning weights,method for assessing
and subsequently water quality
calculating involvesindex
a composite computing sub-
to evaluate
index quality.
water data, assigning weights,method
The calculation and subsequently
outlined bycalculating a composite
Liu et al. [12] index to evaluate
is as follows:
water quality. The calculation method outlined by Liu et al. [12] is as follows:
Construct the initial judgment matrix R
Water 2025, 17, 276 4 of 17

Construct the initial judgment matrix R

 
C11 C12 C1n
C ···
 21 C22 C2n 

R= .. ..  = R Cij mn
..  (1)
. . . 


Cm1 Cm2 ··· Cmn

where: m—number of sampling points; n—number of evaluation indicators.

(1) Calculate the index
Each test value is converted to a multiple of the standard value based on the agricul-
tural irrigation water quality standard, as depicted in Equation (2):

Qij = Cij /Si (2)

In the Equation, Qij signifies the sub-index of the ith for monitoring point j; Cij is the
actual value of the ith for monitoring point j; Si denotes the standardized value of the
i-th indicator.
(2) Calculation of weights
Weights represent the impact of evaluation elements on the degree of water contamina-
tion. Firstly, the entropy value is utilized to standardize the detection value (Equation (3))
and derive the corresponding entropy value, referenced as ei (Equation (4)). Subsequently,
the initial weights are calculated, and finally, the individual indicator weights are normal-
ized (Equations (5) and (6)).

Pij = Cij /(Ci1 + Ci2 + · · · + Cim ) (3)

1 m
∑


ei = − 1
Pij ·lnPij (0 ≤ ei ≤ 1) (4)
lnm
wi′ = 1 − ei (5)
n
wi = wi′ /∑1 wi′ (6)

In the Equation, Pij represents the normalized detection value, ei signifies the entropy
value of the ith index, mm denotes the number of sampling points, wi′ stands for the initial
weight of the ith index, wi indicates the normalized weight of the ith index, and n is the
number of evaluation indices.
(3) Calculate the composite index EWQI:

n
QEWQI = ∑1 wi ·Qij (7)

In the Equation, QEWQI represents the comprehensive index value for the jth sampling
point; Qij denotes the sub-index of the ith indicator at the jth monitoring point; n signifies
the number of assessment indicators.

2.3.2. Sodium Adsorption Ratio (SAR) and Soluble Sodium Percentage (Na%)
There is a correlation between the sodium adsorption ratio of irrigation water and
the soil’s sodium adsorption, making it a useful indicator of the risk of sodium or alkali in
water affecting the soil. The ratio is commonly calculated as shown in Equation (8) [13]:
r 
+
QSAR = Na / Ca2+ + Mg2+ /2 (8)
Water 2025, 17, 276 5 of 17

The qualifying equations in the water quality classification chart are as follows
(Equations (9)–(11)):
High: S = 43.75 − 8.87(logC) (9)

Medium: S = 31.35 − 6.66(logC) (10)

Low: S = 18.87 − 4.44(logC) (11)

where: S—Sodium Adsorption Ratio (SAR); C—Conductivity, us/cm; log—Logarithmic

with base 10.
Na% serves as a crucial indicator for assessing the potential alkali-related harm from
irrigation water; a higher Na% a value signifies an increased risk of alkali damage. Utilizing
such groundwater for irrigation can trigger cation exchange on the soil surface, with
Na+ being adsorbed by the soil and displacing Ca2+ and Mg2+ , thereby diminishing soil
permeability and causing inadequate drainage. The corresponding formula is presented
below [14]:
Na+
Na% = × 100% (12)
Ca2+ + Mg2+ + Na+ + K +
The proportion of sodium ions in irrigation water relative to the total cation concen-
tration is commonly denoted as the soluble sodium percentage (Na%). Regarding sodium
hazards, water with a soluble sodium percentage below 60% is suitable for irrigation, while
levels exceeding 80% are unsuitable for this purpose. Water samples are categorized based
on conductivity into four groups: water with a conductivity below 250 µs/cm is highly
suitable for irrigation, water in the 250–750 µs/cm range is suitable, water ranging from
750 to 2250 µs/cm is classified for reserved irrigation, and water exceeding 2250 µs/cm is
unsuitable for irrigation.
Wilcox graph (1955) [15] and USSL graph (1954) [16] technique are employed to
demonstrate the accuracy and classification of water utilized for irrigation consistently [17].
The USSL graph features a logarithmic scale of EC in µS/cm on the X-axis and SAR on the
Y-axis, delineating different water quality classes: higher, high, mid, and low. In contrast,
the Wilcox plot uses the standard EC scale on the X-axis and Na% on the Y-axis [18],
illustrating five water quality divisions: Unsuitable, Retained, Suitable, Very Suitable, and
Over Irrigation. These graphs were constructed utilizing Diagramme software (6.60) [19].

3. Results and Discussion

3.1. Descriptive Statistics
As shown in Table 2, surface water predominantly contains Ca2+ cations along with
SO4 and HCO3 − anions. Conversely, groundwater is characterized by NO3 − and SO4 2−
2−

anions alongside Ca2+ and Na+ cations. In the study area, groundwater exhibited a pH
range of 6.86 to 7.99, averaging 7.51, while surface water showed a pH range of 7.48 to 7.98,
with an average of 7.81, demonstrating predominantly weak alkalinity. The groundwater
TDS ranged from 358.26 mg/L to 4154.21 mg/L, with a mean concentration of 1340.79 mg/L.
In the study area, freshwater (TDS < 1 g·L−1 ), brackish water (1 g·L−1 < TDS < 3 g·L−1 ),
and salty water (3 g·L−1 < TDS < 10 g·L−1 ) constituted 31.03%, 65.52%, and 3.45% of
the groundwater samples, respectively. Brackish water predominantly dominates the
shallow groundwater in this area. The TDS in surface water ranged from 543.61 mg·L−1 to
1203.28 mg·L−1 , averaging 875.33 mg·L−1 . In surface water samples, freshwater constituted
60%, while brackish water made up 40%. The total hardness (TH) of water bodies in the
region exhibited elevated levels. Groundwater TH varied between 235.13 mg·L−1 and
1606.10 mg·L−1 , averaging 759.91 mg·L−1 , while surface water exhibited TH levels ranging
from 393.36 mg·L−1 to 639.14 mg·L−1 , with a mean value of 528.84 mg·L−1 . The coefficients
Water 2025, 17, 276 6 of 17

of variation analysis revealed that concentrations of Na+ , Cl− , and NO3 − in groundwater
surpassed 100%, indicating significant fluctuations in its quality. In contrast, surface water
exhibited coefficients of variation below 100%, signifying greater stability in its quality
compared to groundwater.

Table 2. Statistical results of water chemical indicators of water samples in the DBA.

pH TDS TH Na+ SO4 2− Cl− HCO3 − NO3 −

Standard Value 6.5–8.5 ≤1000 ≤450 ≤200 ≤250 ≤250 ≤250 ≤88.6
Minimum 6.86 358.26 235.13 24.7 51.65 27.69 88.62 29.48
Maximum 7.99 4154.21 1606.10 678.00 700.00 1030.91 480.61 1820.0
Mean value 7.51 1340.79 759.91 115.68 246.81 231.15 200.74 369.67
Groundwater
Standard deviation 0.25 737.96 324.80 128.84 126.06 234.12 101.89 362.056
Exceedance rate (%) 0 68.97 82.76 17.24 34.48 24.14 20.69 79.31
Coefficient of variation (%) 3.3 55.04 42.74 111.38 51.08 101.28 50.76 97.94
Minimum 7.48 543.64 393.36 45.26 132.94 84.61 187.47 11.90
Maximum 7.98 1203.28 639.14 150 256.83 291.63 565.82 68.27
Surface Mean value 7.81 875.33 528.84 90.16 191.54 172.98 361.39 43.58
water Standard deviation 0.20 302.63 129.96 44.48 54.04 88.75 187.73 21.79
Exceedance rate (%) 0 40.00 60.00 0 20.00 20.00 60.00 0
Coefficient of variation (%) 3.0 35.0 25.0 49.0 28.0 51.0 52.0 50.0
Note: pH is dimensionless, and the rest of the indicators are in mg·L−1 .

3.2. Spatial Distribution of Major Ions

Sampling points for surface water were arranged at three locations along the Dagu
River and two locations along the southeast drainage channel. The order of cation con-
centration content is Ca2+ > Na+ > Mg2+ > K+ . Water samples from the upstream river
and two drainage canals exhibited comparable Ca2+ and Mg2+ levels, with Ca2+ concen-
trations at 161.80 mg·L−1 , 180.30 mg·L−1 , and 164.30 mg·L−1 , and Mg2+ concentrations
at 51.60 mg·L−1 , 45.94 mg·L−1 , and 49.86 mg·L−1 , in that order. The Mg2+ concentrations
measured were 51.60 mg·L−1 , 45.94 mg·L−1 , and 49.86 mg·L−1 , significantly surpassing
standard limits. Na+ concentrations at the drainage-canal-sampling sites notably exceeded
those at the river sampling sites, measuring 112.80 mg·L−1 and 150.00 mg·L−1 . In terms of
anions, the overall distribution followed the trend HCO3 − > SO4 2− > Cl− > NO3 − , decreas-
ing towards the river. The analysis revealed a slightly basic aquatic setting particularly in
the southeastern area. Particularly, the drainage canal on the southeast side exhibits notably
higher HCO3 − concentrations compared to other surface water sampling points. Moreover,
higher mass concentrations of HCO3 − in surface water correspond to lower levels of NO3 −
in the water. Chloride (Cl− ) and sulfate (SO4 2− ) exhibited a positive correlation, with Cl−
concentrations exceeding those of SO4 2− . This trend aligned with the distribution of the
cation Na+ , confirming the incidence of secondary soil salinization.
Figure 2a,b demonstrate consistently elevated Ca2+ and Mg2+ concentrations across
the study area, with Ca2+ levels notably higher in the central residential and farm shed
zones compared to the river and southern farm shed areas. Meanwhile, Mg2+ concentra-
tions exhibit a more uniform spatial distribution. In Figure 2c, higher Na+ concentrations in
the eastern region echo the distribution of Cl− concentrations, possibly linked to human ac-
tivities. Figure 2d highlights regions with elevated K+ concentrations, likely attributable to
algal blooms within the water, indicating signs of water body eutrophication and resulting
in increased K+ levels.
Water 2025, 17, x FOR PEER REVIEW 7 of 17
Water 2025, 17, 276 7 of 17

Figure 2. Cont.
Water 2025, 17, x FOR PEER REVIEW 8 of 17
Water 2025, 17, 276 8 of 17

Figure 2. (a,b) are the spatial distribution of surface water cation pie and anion pie, respectively;
Figure 2. (a,b) are the spatial distribution
2+
of2+surface
+
water
+ −
cation−pie and
2−
anion pie,−respectively;
(c–j) are the spatial distribution of Ca , Mg , Na , K , Cl , NO3 , SO4 and HCO3 , respectively.
(c–j) are the spatial distribution of Ca2+, Mg2+, Na+, K+, Cl−, NO3−, SO42− and HCO3−, respectively.
According to Figure 2e, the chloride (Cl− ) concentration is notably elevated in the
According
eastern region,tospecifically
Figure 2e,measuring
the chloride1030.91 (Clmg ·L−1 at point LX07,
−) concentration is notably
indicatingelevated in the
significant
eastern region, specifically
anthropogenic influences.measuring 1030.91region
Being a semi-arid mg·Lknown
−1 at point LX07, indicating
for agriculture, significant
this area exten-
sively utilizes
anthropogenic open-air and
influences. greenhouse
Being a semi-arid cultivation. Excessive
region known use of chemical
for agriculture, thisfertilizers
area exten-
andutilizes
sively pesticides, coupled
open-air and with improper irrigation
greenhouse cultivation. practices, leads
Excessive to of
use soilchemical
salinization due
fertilizers
andtopesticides,
increased saltcoupledcontent.withFigure 2f illustrates
improper irrigation thepractices,
interpolation
leadsoftogroundwater nitrate
soil salinization due
(NO − ) concentrations. The average NO − concentration is 369.67 mg·L−1 , with a peak
3 3
to increased salt content. Figure 2f illustrates the interpolation of groundwater nitrate
of 1820.0 mg·L−1 . In the west–central region, The concentration of NO − ranges from
(NO3−) concentrations.
− 1
The average − 1
NO3− concentration is 369.67 mg·L−13, with a peak of
171.86 mg·L to 825.03 mg·L , while the majority of the area shows concentrations
1820.0 mg·L−1. In −the west–central region, The concentration of NO3− ranges from 171.86
above 1
50 mg·L . These levels significantly surpass the groundwater NO3 − standard of
mg·L to 825.03
−1 mg·L , while the majority of the area shows concentrations above 50
−1
88.6 mg·L−1 , impeding crop growth and posing a threat to the groundwater environment.
mg·L . These levels significantly surpass the
−1 groundwater NO3− standard of 88.6 mg·L−1,
In Figure 2g, the distribution of SO4 2− concentration mirrors that of the NO3 − con-
impeding
centration,cropdisplaying
growth and posing
a high meana value
threatofto246.81
the groundwater environment.
mg·L−1 and peaking at 700.00 mg·L−1
inIn Figure 2g, the region.
distribution of SO 4 concentration mirrors that of the NO3− concen-
2−
the west–central Because groundwater contaminated by domestic wastewater
tration, displaying
and natural a high(manure,
fertilizers mean value of 246.81
a source mg·Lnitrogen)
of organic −1 and peaking at 700.00 mg·L−1 in the
is typically connected with
west–central region. 2
Because− groundwater contaminated
an enrichment of SO4 [20–22], a hypothesis arises linking nitrate by domestic wastewater
pollution and
to the pes-
natural
ticidesfertilizers (manure,
and fertilizers a source
washed awayofduring
organic nitrogen)
farmland is typically
cultivation connected
in the researchwith
area.an
Figure 2hof illustrates the distribution of HCO −
enrichment SO4 [20–22],
2− a hypothesis 3 concentrations
arises linking nitratein groundwater,
pollution to highlighting
the pesticides
a peak value near the drainage canal in the southeast.
and fertilizers washed away during farmland cultivation in the research area. Figure 2h
illustrates the distribution of HCO3− concentrations in groundwater, highlighting a peak
3.3. Hydrochemical Type
value near the drainage canal in the southeast.
3.3.1. Kurlovian and Shukarevian Type
The analysis
3.3. Hydrochemical of water chemistry reveals a notable rise in the nitrate (NO3 − ) con-
Type
centration with increased chemical pesticide usage. This increase exposes limitations in
3.3.1. Kurlovian and Shukarevian Type
traditional water chemistry classifications. To resolve this issue, a novel water chemistry
The analysis
classification of water
method chemistry based
is introduced reveals
onathe
notable rise inofthe
principles nitrate
Kurllov and (NO 3−) concentra-
Schlumberger
tionclassifications
with increased [23].chemical
When the pesticide usage. This
milliequivalents −
increase
of NO exposes limitations in tradi-
3 in groundwater exceed 25% of
the total ion content, surpassing that of other ions, this water type can
tional water chemistry classifications. To resolve this issue, a novel water chemistry clas- be denoted as
“NO3 ·SO
sification 4 -Ca”,is
method visually indicating
introduced basedthe
on highest nitrate of
the principles concentration.
Kurllov and For samples with
Schlumberger clas-
NO − milliequivalents below 25%, categorization can be “Cl-Ca·Na” or “HCO ·SO -Ca”,
sifications
3 [23]. When the milliequivalents of NO3− in groundwater exceed 25%3 of the 4 total
according to this classification. Surface water can be classified as “HCO 3
ion content, surpassing that of other ions, this water type can be denoted as “NO3·SO4- · SO4 -Ca”. Cast the
sampling point test data onto a Piper trilinear chart
Ca”, visually indicating the highest nitrate concentration. For samples with NO3 mil- −

liequivalents below 25%, categorization can be “Cl-Ca·Na” or “HCO3·SO4-Ca”, according

to this classification. Surface water can be classified as “HCO3·SO4-Ca”. Cast the sampling
point test data onto a Piper trilinear chart

3.3.2. The Piper Diagram

A Piper trilinear diagram is employed to delineate the principal ionic compositions
and hydrochemistry of groundwater [24]. The sampled data points were cast on a Piper
 some distribution. Consequently, the predominant hydrochemical type in the DBA is
identified as SO4·Cl-Ca·Mg.
Water 2025, 17, 276 Within the region, NO3− concentrations are notably elevated, surpassing9 the of 17 capabil

ities of the Piper trilinear diagram to comprehensively depict the local water chemistry
To address this, distinct color coding was utilized to differentiate between high and low
3.3.2. The Piper Diagram
NO3− levels, facilitating a thorough examination of the region’s water chemistry profiles
A Piper trilinear diagram is employed to delineate the principal ionic compositions
Of the samples, 38.24% of groundwater and all surface water samples displayed NO3
and hydrochemistry of groundwater [24]. The sampled data points were cast on a Piper
concentrations
diagram (Figure below
3). The 100 mg/L;
analysis meanwhile,
reveals that most14.71% of groundwater
water samples samples
are positioned within exhibited
concentrations
the I region, withexceeding 600 sampling
cation triangle mg/L. Notably, a discernible
points located relationship
in regions A and B. Inemerged
the anionbetween
the proximity
triangle of sampling
area, most sampling points to the
points are summits
in region of Zoneregions
B, although I and Zone
E andAGand
alsoelevated
show NO3
levels,distribution.
some highlightingConsequently,
a correlationthe
between nitratehydrochemical
predominant concentrationtypeand in
calcium–magnesium
the DBA is
levels. as SO4 ·Cl-Ca·Mg.
identified

Figure3.3.Piper
Figure Piperdiagram
diagramin in
thethe
DBA.
DBA.

Within the region, NO3 − concentrations are notably elevated, surpassing the capabili-
3.4. The Interrelationships Among Various Chemical Indicators
ties of the Piper trilinear diagram to comprehensively depict the local water chemistry. To
There
address is a correlation
this, distinct between
color coding the to
was utilized chemical composition
differentiate of and
between high low NO3 − and its
groundwater
sources.
levels, Researchers
facilitating often examination
a thorough employ the of interrelationships
the region’s wateramong chemical
chemistry profiles.components
Of the to
samples, 38.24% of groundwater and all surface water samples displayed NO − concentra-
unveil the origins of ions [25]. The water chemistry data were analyzed 3 for correlations
tions below 100 mg/L; meanwhile, 14.71% of groundwater samples exhibited
using SPSS software (28.0), resulting in a correlation coefficient matrix for the chemica concentra-
tions exceeding
components 600 mg/L.
(Figure Notably,
4). Nitrate a discernible
(NO relationship emerged between the prox-
3−) shows significant correlations at the 0.01 level (two
imity of sampling points to the summits of Zone I and Zone A and elevated NO3 − levels,
tailed) with TDS, Ca2+, Mg2+, and HCO3−, with respective coefficients of 0.69, 0.87, 0.67, and
highlighting a correlation between nitrate concentration and calcium–magnesium levels.
−0.45. This suggests that NO3− is highly correlated with these ions. The correlation between
CO3The
3.4. − and Na+, K+, and Among
Interrelationships Cl− at Various
the 0.01Chemical
significance level is notably strong, with respective
Indicators
correlation
There iscoefficients of between
a correlation 0.62 and the
0.52,chemical
indicating homogeneity
composition with HCO3−and
of groundwater for these
its ions
Similarly,
sources. SO4 exhibits
2−
Researchers often significant
employ the correlations withamong
interrelationships Ca and
2+ Mg at
2+
chemical the 0.01 significance
components to
unveil the origins of ions [25]. The water chemistry data were analyzed for correlations
level, with correlation coefficients of 0.85 and 0.81, indicating that the primary ions in the
using
studySPSS
area’ssoftware (28.0), resulting
groundwater in a correlation
likely stem coefficient matrix
from the dissolution for the chemical
of evaporite rocks (gypsum
components (Figure 4). Nitrate (NO − ) shows significant correlations at the 0.01 level
and silicate rocks. 3
(two-tailed) with TDS, Ca2+ , Mg2+ , and HCO3 − , with respective coefficients of 0.69, 0.87,
0.67, and −0.45. This suggests that NO3 − is highly correlated with these ions. The cor-
relation between CO3 − and Na+ , K+ , and Cl− at the 0.01 significance level is notably
strong, with respective correlation coefficients of 0.62 and 0.52, indicating homogeneity
with HCO3 − for these ions. Similarly, SO4 2− exhibits significant correlations with Ca2+ and
Mg2+ at the 0.01 significance level, with correlation coefficients of 0.85 and 0.81, indicating
Water 2025, 17, 276 10 of 17
Water 2025, 17, x FOR PEER REVIEW 10 of 17

Water 2025, 17, x FOR PEER REVIEWthat the primary ions in the study area’s groundwater likely stem from the dissolution
10 of of
17
evaporite rocks (gypsum) and silicate rocks.

Figure 4. Matrix of correlation coefficients for water chemical constituents.

Figure 4. Matrix of correlation coefficients for water chemical constituents.

Figure 4. Matrix of correlation coefficients for water chemical constituents.
3.5. Factors Controlling the Hydrochemical Characteristics
3.5. Factors
3.5.1. Controlling the Hydrochemical Characteristics
Rock Weathering
3.5. Factors Controlling the Hydrochemical Characteristics
3.5.1. Rock Weathering
3.5.1.Evaporative processes, atmospheric precipitation, and rock weathering are the key
Rock Weathering
factors that impactprocesses,
Evaporative the chemical atmospheric precipitation,
composition and
of water [12]. rock
The weathering
Gibbs diagramare the key
model es-
Evaporative processes, atmospheric precipitation, and rock weathering are the key
factors that
tablished by impact the chemical
Gibbs (1970) [26] wascomposition
employed toofpinpoint
water [12]. The Gibbs
the primary diagram
factors model
impacting
factors that impact the chemical composition of water [12]. The Gibbs diagram model es-
established by
groundwater Gibbs (1970)
chemistry [27]. [26] was
Figure employed
5 shows to pinpoint the
the distribution primary
of water factors
samples impacting
in the Gibbs
tablished by Gibbs (1970) [26] was employed to pinpoint the primary factors impacting
groundwater
diagram chemistry
within the study [27]. Figure
area, 5 shows the distribution
predominantly of water
located in the samples in the
rock-weathering Gibbs
control
groundwater chemistry [27]. Figure 5 shows the distribution of water samples in the Gibbs
diagram within the study area, predominantly located in the rock-weathering
zone. This indicates a significant influence of water–rock interactions on the hydrochem- control zone.
diagram within
Thischaracteristics
the study
indicates a significant
area,
influence
predominantly located in the rock-weathering control
ical of the study area. of water–rock
However, interactions
some on theare
water samples hydrochemical
also affectedchar-
by
zone. Thisof
acteristics indicates
the studya significant
area. influence
However, some of water–rock
water samples interactions
are also on the
affected by hydrochem-
evaporation
evaporation crystallization processes, potentially linked to human activities and agricul-
ical characteristics
crystallization of the study area. However, some water samples are also affected by
tural irrigation.processes, potentially linked to human activities and agricultural irrigation.
evaporation crystallization processes, potentially linked to human activities and agricul-
tural irrigation.

Gibbs diagram of water in the study + /(Na + +Ca2+ ), (b) TDS

Figure5.5.Gibbs
Figure diagram of water in the study area.area. (a) vs.
(a) TDS TDS Navs. Na++Ca
+/(Na 2+), (b) TDS vs. Cl–/(Clvs.
–

Cl– /(Cl– +HCO – ).

+HCO3–). 3
Figure 5. Gibbs diagram of water in the study area. (a) TDS vs. Na+/(Na++Ca2+), (b) TDS vs. Cl–/(Cl–
3.5.2. 3Ion
+HCO –). Ratios
3.5.2. Ion Ratios
Ion ratios play a vital role in discerning the rock-weathering mechanisms that influence
Ion
3.5.2. Ionratios play a vital role in discerning the rock-weathering mechanisms that influ-
Ratios
the hydrochemical properties of groundwater [28]. Water samples in the DBA are primarily
ence the hydrochemical properties of groundwater [28]. Water samples in the DBA are
distributed within
Ion ratios playthe control
a vital roleranges of silicate
in discerning theand carbonate rocks
rock-weathering (Figure 6). that
mechanisms The distri-
influ-
primarily distributed within the control ranges of silicate and carbonate rocks (Figure 6).
bution of water-sampling points, as illustrated in Figure 6a, demonstrates a
ence the hydrochemical properties of groundwater [28]. Water samples in the DBA are skew towards
The distribution of water-sampling points, as illustrated in Figure 6a, demonstrates a skew
primarily distributed within the control ranges of silicate and carbonate rocks (Figure 6).
towards silicate rocks based on cation ratios. From the perspective of anion ratios (Figure
The distribution of water-sampling points, as illustrated in Figure 6a, demonstrates a skew
towards silicate rocks based on cation ratios. From the perspective of anion ratios (Figure
Water 2025, 17, 276 11 of 17

silicate rocks based on cation ratios. From the perspective of anion ratios (Figure 6b), the
water samples in the study area fall within the spectrum between evaporitic salt rocks
and silicate rocks. This observation suggests that evapotranspiration plays a role in water
chemistry, with all surface and groundwater components primarily originating from silicate
rocks [29].

2+
\Na + 2+
\Na + – +
6. End-member
Figure 6.
Figure End-memberdiagram
diagramin in
thethe
DBA. (a) (Mg
DBA. (a) (Mg ) vs.
2+\Na +) (Ca
vs. (Ca ), (b)
2+\Na +),(HCO 3 \ Na
(b) (HCO ) vs.
3–\ Na+) vs.
(Ca2+ \Na+ ).
(Ca2+\Na+).
3.5.3. Main Ion Sources
The dissolution of Na+ and Cl− is primarily associated with salt rock dissolution.
When sampling points are predominantly positioned along the 1:1 line, it indicates that Na+
and Cl− in surface water primarily originate from rock salt dissolution. In Figure 7a, most
samples are concentrated below the 1:1 line, indicating that the dissolution of salt minerals
is not the primary source of Na+ and Cl− ions. Furthermore, the clustering of samples at
lower positions below the 1:1 line indicates potential influences of cation exchange and
silicate weathering [30]. In the study area, the γ (Cl− ) content is slightly higher than the γ
(Na+ ) content, indicating that besides the dissolution of salt rocks, chloride (Cl− ) may have
other sources influenced by human activities, for example, the application of pesticides and
fertilizers and wastewater discharge.
If only gypsum (CaSO4 ·2H2 O) is dissolved in groundwater, the milliequivalent ratio
of γ(SO4 2− ) to γ(Ca2+ ) should be 1:1 [31]. As shown in Figure 7b, most water samples
in the study area are distributed on both sides of γ(SO4 2− ): γ (Ca2+ ) = 1:2, indicating
that the γ(Ca2+ ) in the study area originates not only from gypsum dissolution but also
suggests a significant influence from calcium-rich rock weathering during water–rock
interactions. The interrelationship between γ(Ca2+ +Mg2+ ) and γ(HCO3 − +SO4 − ) can verify
the effects of mineral weathering and ion exchange reactions. If calcium and magnesium
originate from the weathering of carbonate, sulfate minerals (gypsum, anhydrite), and
silicate minerals, both will be balanced by HCO3 − +SO4 − [32]. In Figure 7c, approximately
86.1% of samples show a higher concentration of γ (Ca2+ + Mg2+ ) than γ (HCO3 − + SO4 − ),
indicating that the dissolution of silicate rocks significantly influences the water’s chemical
composition, with silicates dissolving into groundwater through chemical weathering.
A small proportion of samples (approximately 13.9%) fall below the 1:1 line, indicating
the influence of carbonate rock weathering on the hydrochemical environment [33,34].
Additionally, Figure 7d illustrates that the sampling points predominantly align with the
1:1 line, suggesting potential additional sources of Mg2+ and Ca2+ in the water, such as
dissolution of ion exchange or silicate rocks [35].
The intensive agricultural cultivation and dense human activities in the study area
indicate a significant impact of human activities on the hydrochemical environment. Nitrate
is a crucial contaminant in groundwater, likely originating from agricultural practices
 Water 2025, 17, 276 12 of 17

and domestic sewage. The ratio between (SO4 2− /Ca2+ ) and (NO3 − /Ca2+ ) can serve as
an indicator of human activities’ impact on groundwater [36]. As depicted in Figure 6,
the increase in NO3 − /Ca2 + and SO4 2− /Ca2+ values indicates the influence of domestic
sewage disposal, agricultural practices, and industrial activities on groundwater chemistry.
The area under study is notably more influenced by agricultural cultivation and domestic
Water 2025, 17, x FOR PEER REVIEW wastewater. Due to anthropogenic influences, the groundwater in this region exhibits 2 of 2
elevated levels of NO3 − , Cl− , and SO4 2− [37,38]. The ratios of NO3 − /Na+ and Cl− /Na+
tend to rise. As shown in Figure 7, most samples are located within the agricultural impact
end-member, indicating a significant influence of agricultural activities on the groundwater
of the DBA.

2+ 2− 2+ 2+ 2− −
Figure
Figure 7. Ion
7. Ion ratiodiagrams.
ratio diagrams. (a)
(a)Na+
Na+vs.vs.
Cl;Cl;
(b) (b)
Ca Ca
vs.2+ SO 42−(Ca
; (c)
vs.4 SO +Mg2++Mg
; (c) (Ca ) vs.2+(SO
) vs. 42−+HCO
+HCO
4 (SO 3 ); 3−);
(d) (Ca2+ +Mg2+ ) vs. HCO3 − ; (e) (NO3 − \Ca2+ ) vs. (SO4 2− \Ca2+ ); (f) (NO3 − \Na+ ) vs. (Cl− \Na+ ).
(d) (Ca2++Mg2+) vs. HCO3−; (e) (NO3−\Ca2+) vs. (SO42−\Ca2+); (f) (NO3−\Na+) vs. (Cl−\Na+).
3.6. Water Quality Assessment
The fundamental concept behind EWQI involves using entropy values to ascertain the
weights of assessment indices and converting extensive water quality data into reflective
values of water quality status [39]. The entropy value method is noted for its strong
objectivity and its capacity to efficiently rectify errors in weight calculations [40]. Therefore,
it is more reasonable to use EWQI.
The agricultural cultivation practices in the study area involve extensive use of fertiliz-
ers and pesticides during cultivation. The primary sources of irrigation water are the local
surface and groundwater. Therefore, evaluating the quality of groundwater for irrigation
holds significant importance for agricultural cultivation and provides a scientific basis
for guidance.
Water 2025, 17, 276 13 of 17

3.6.1. Evaluation of Irrigation Water Quality Based on Groundwater Standards

The evaluation results of the 34 water sampling points in the study area based on
the EWQI criteria fall into five categories: EWQI < 25, 25 < EWQI < 50, 50 < EWQI < 100,
100 < EWQI < 150, and EWQI > 150, representing grades I, II, III, IV, and V, respectively,
where grades IV and V are deemed unsuitable for irrigation. The analysis reveals that
none of the total sampled water falls into grade I, accounting for 0%; grade II includes
six samples (four groundwater samples, two surface water samples), representing 17.65%;
grade III comprises eleven samples (nine groundwater samples, two surface water samples),
amounting to 32.35%; grade IV consists of eleven samples (all groundwater samples), also
at 32.35%; and grade V encompasses six samples (all groundwater samples), making
up 17.65%.
The assessment results indicate that most of the study area falls under Class III and
Class IV water categories. Class III water is predominant in the upper reaches and southern
regions of the rivers, interspersed with isolated Class II water sources. The central areas
housing clustered villages and greenhouse farming sites are classified as Class IV water,
while the water quality in the Yujiaxiaoli Village to Dianbu Town region is categorized
as Class V. Agricultural activities represent a primary source of water system pollution,
introducing nutrients (utilized as fertilizers in crop production) and plastics (employed
for crop covering), among other contaminants [41]. Consequently, the water quality in
surface [42] and groundwater [43,44] is progressively deteriorating.

3.6.2. Evaluation of Irrigation Water Quality Based on Farmland Safety Standards

Agricultural practices in the study area are extensive, involving significant usage of
chemical fertilizers and pesticides. The primary sources of irrigation water are derived from
the Dagu River and groundwater. Assessing the quality of irrigation water sourced from
groundwater is crucial for agricultural cultivation in this context, offering a foundational
framework for informed scientific guidance.
The SAR and the Na% serve as indicators of the harm caused by excessive sodium
content in irrigation water. Elevated levels of Na+ in irrigation water can detrimentally
affect the physicochemical properties of soil, leading to issues like soil compaction and
reduced permeability [45], which in turn affect plant growth. Based on statistical analysis
of hydrochemical data, a water quality classification diagram for irrigation water was
generated using the USSL and Wilcox graphical methods.
The SAR results, as shown in Figure 8a, indicate that in groundwater samples, 55.18%
fell within the C3 zone, while 34.48% and 10.34% of samples fell within the C4 and C2
zones, respectively, with no samples in the C1 zone. Among the groundwater samples,
distribution in the S1, S2, S3, and S4 zones was 20.69%, 48.28%, 10.34%, and 20.69%,
respectively. Surface water samples all fell within the C3 zone, with distributions of 40%,
20%, and 40% in the S1, S2, and S3 zones, respectively, and no samples in the S4 zone. The
majority of both groundwater and surface water samples exhibit relatively low alkalinity
levels but elevated soluble salt concentrations. Utilizing these waters for irrigation may
contribute to soil salinization, potentially impacting crop growth. Overall, groundwater
samples from the study area, falling within the C2-S1, C3-S1, and C3-S2 categories, are
deemed suitable for irrigation purposes, constituting 65.52% of the total samples, with
groundwater accounting for 47.06% and surface water for 8.82%.
The results for Na% are depicted in Figure 8b. The EC values of samples in the
DBA varied from 537.39 to 3394.01 µs/cm, with an average of 1768.68 µs/cm. Only
one groundwater sample had a sodium content exceeding 50%, while the rest were below
this threshold. Samples from areas categorized for suitable irrigation, marginal irrigation,
and unsuitable irrigation constituted 8.8%, 61.79%, and 29.41% of all the samples, respec-
 Water 2025, 17, 276 14 of 17
Water 2025, 17, x FOR PEER REVIEW 14 of

tively. Notably, all surface water samples were within the marginal irrigation category.
Situated in a semi-arid region, waters with EC values lower than the average were also
deemed suitable
considered suitablefor
for irrigation purposes,
irrigation. The analysis constituting 65.52% of the55.88%
indicates that approximately total ofsamples,
the wi
groundwater
water could beaccounting for 47.06%
used for irrigation and surface water for 8.82%.
purposes.

Figure 8. Water quality classification (a) SAR (C for salinity class, S for alkalinity class); (b) Na%.
Figure 8. Water quality classification (a) SAR (C for salinity class, S for alkalinity class); (b) Na%.
4. Conclusions
The results for Na% are depicted in Figure 8b. The EC values of samples in the DB
Groundwater and surface water serve as primary agricultural irrigation sources in the
varied
DBA. Anfrom 537.39 toof3394.01
investigation µs/cm,
five surface with
water an average
samples of 1768.68
and twenty-nine µs/cm. Only
groundwater one groun
samples
water sample had
were conducted to aevaluate
sodiumits content exceeding
hydrochemical 50%, while
attributes the rest were
and suitability below this thres
for irrigation
old. Samples
purposes, from areas
employing categorized
methods forSAR,
like EWQI, suitable
and Na%irrigation, marginal
for water irrigation, and u
quality assessment.
The findings
suitable are as follows:
irrigation constituted 8.8%, 61.79%, and 29.41% of all the samples, respective
(1) In the DBA,
Notably, all surface water water samples
samples exhibit a pH range
were within between irrigation
the marginal 6.86 and 7.99, with Situat
category.
an average of 7.55, indicating weak alkalinity. The TDS concentration in the study zone
in a semi-arid region, waters with EC values lower than the average were also consider
varies from 358.26 mg·L−1 to 4154.21 mg·L−1 , with an average of 1340.79 mg·L−1 . The un-
suitable for irrigation. The analysis indicates that approximately 55.88% of the water cou
derground water shows a cation order of Ca2+ > Na+ > Mg2+ > K+ and an anion sequence of
be
NOused
− for irrigation
3 > SO4
2− > Cl− > purposes.
HCO3 − . The cationic composition of surface water mirrors that of
groundwater, although notable discrepancies are found in the anionic content. The descend-
4.ingConclusions
order of anionic mass concentrations is HCO3 − > Cl− > SO4 2− > NO3 − . Analysis through
Piper diagrams reveals a prevailing water chemistry profile in the DBA characterized by
Groundwater and surface water serve as primary agricultural irrigation sources
a dominance of SO4 ·Cl-Ca·Mg type.
the DBA. An investigation of five surface water samples and twenty-nine groundwat
(2) Chemical control factors analysis indicates that all natural elements and anthro-
samples were conducted
pogenic activities to evaluate
significantly impact the itshydrochemical
hydrochemical attributes of
characteristics and suitability
surface and for ir
gation purposes,
groundwater. employing
The chemical methodsoflike
environment the EWQI,
study areaSAR, and Na%
is notably for water
influenced quality asse
by natural
ment.
processesThelike
findings aredissolution
evaporite as follows:(gypsum), silicate rock weathering, cation exchange,
and (1)
carbonate rock dissolution.
In the DBA, water samples Human activities,
exhibit particularly
a pH range industrial
between activities,
6.86 and notably
7.99, with
influence the hydrochemical characteristics through factors like agricultural
average of 7.55, indicating weak alkalinity. The TDS concentration in the study zone var cultivation
and domestic wastewater discharge.
from 358.26 mg·L−1 to 4154.21 mg·L−1, with an average of 1340.79 mg·L−1. The undergrou
(3) Calculating the quality of water used for irrigation reveals that 65.52% of the water
water shows a cation order of Ca2+ > Na+ > Mg2+ > K+ and an anion sequence of NO3− > SO
is suitable for irrigation, with groundwater constituting 47.06% and surface water 8.82%.
>The
Cl−Na%> HCO 3−. The cationic composition of surface water mirrors that of groundwat
analysis indicates that 8.8% of water samples are suitable for irrigation, while
although
55.88% arenotable discrepancies
usable. Irrigation are should
decisions foundalignin the anionic
with actualcontent.
production The descending order
circumstances,
anionic massrational
establishing concentrations
upper limitsisfor
HCO 3 > Cl >levels.
−
groundwater − SO4 > NO3 . Analysis through Piper d
2− −

(4) By establishing a monitoring and

grams reveals a prevailing water chemistry profiledata analysis system
in theforDBA
both groundwater
characterized andby a dom
surface water, real-time
nance of SO4·Cl-Ca·Mg type. observation of water resources fluctuations is enabled. This system
integrates agricultural resources, advocates for efficient water-saving irrigation methods
(2) Chemical control factors analysis indicates that all natural elements and anthr
like drip and spray irrigation, and introduces quality equipment to reduce water wastage
pogenic activities significantly impact the hydrochemical characteristics of surface a
groundwater. The chemical environment of the study area is notably influenced by nat
ral processes like evaporite dissolution (gypsum), silicate rock weathering, cation e
change, and carbonate rock dissolution. Human activities, particularly industrial acti
ties, notably influence the hydrochemical characteristics through factors like agricultu
Water 2025, 17, 276 15 of 17

and control soil salinization. Additionally, it aims to prevent excessive water resource
exploitation and implement comprehensive measures and planning strategies effectively.

Author Contributions: All authors contributed to the study conception and design. Z.G.: investiga-
tion, form analysis software, methodology, writing—draft. T.H.: concepts, methods, writing—review,
resource acquisition. J.C.: research, resource acquisition. H.T.: investigation, resource acquisition.
M.T.: investigation. Y.N.: investigation. K.L.: Read and approved the final manuscript. All authors
have read and agreed to the published version of the manuscript.

Funding: This study was financially supported by Experimental Study on Salt Blockage Effects and
Mechanisms during Water-Rock Interactions in Brackish Water Transgressions (ZR2020MD109).

Data Availability Statement: The datasets used and/or analyzed during the current study are
available from the corresponding author on reasonable request.

Acknowledgments: We are grateful to the reviewers and editors for their valuable comments on this
article. And, the authors sincerely thank the researchers and staff members for Hydrogeology and
Environmental Geology Survey.

Conflicts of Interest: Zongjun Gao, Tingting Huang, Jinkai Chen, Hong Tian, Menghan Tan, Yiru Niu
and Kexin Lou have no relevant financial or non-financial interests to disclose.

References
1. Emenike, P.C.; Nnaji, C.C.; Tenebe, I.T. Assessment of geospatial and hydrochemical interactions of groundwater quality,
southwestern Nigeria. Environ. Monit. Assess. 2018, 190, 440. [CrossRef] [PubMed]
2. Siebert, S.; Burke, J.; Faures, J.M.; Frenken, K.; Hoogeveen, J.; Dll, P.; Portmann, F.T. Groundwater use for irrigation—A global
inventory. Hydrol. Earth Syst. Sci. Discuss. 2010, 7, 3977–4021. [CrossRef]
3. Li, H.H.; Lu, Y.D.; Zheng, C.; Zhang, X.N.; Zhou, B.; Wu, J. Seasonal and Inter-Annual Variability of Groundwater and Their
Responses to Climate Change and Human Activities in Arid and Desert Areas: A Case Study in Yaoba Oasis, Northwest China.
Water 2020, 12, 303. [CrossRef]
4. Jaime, H. Regulating Agricultural groundwater use in arid and semi-arid regions of the Global South: Challenges and socio-
environmental impacts. Curr. Opin. Environ. Sci. Health 2022, 27, 100341.
5. Subba Rao, N. Spatial distribution of quality of groundwater and probabilistic non-carcinogenic risk from a rural dry climatic
region of South India. Environ. Geochem. Health 2020, 43, 1–23. [CrossRef] [PubMed]
6. Wang, H.L.; Yang, Q.C.; Ma, H.Y.; Liang, J. Chemical compositions evolution of groundwater and its pollution characterization
due to agricultural activities in Yinchuan Plain, northwest China. Environ. Res. 2021, 200, 111449. [CrossRef] [PubMed]
7. Shen, Z.L.; Wang, Y.X. Review and outlook of water-rock interaction studies. Earth Sci.—J. China Univ. Geosci. 2002, 27, 127–133.
8. Guo, G.X.; Hou, Q.L.; Xu, L.; Liu, J.R.; Xin, B.D. Delamination and zoning characteristics of quaternary groundwater in Chaobai
Alluvial-proluvial Fan, Beijing, based on hydrochemical analysis. Acta Geosci. Sin. 2014, 35, 204–210.
9. Zhang, F.C.; Wu, B.; Gao, F.; Du, M.L.; Xu, L.T. Hydrochemical characteristics of groundwater and evaluation of water quality in
arid area of Northwest China: A case study in the plain area of Kuitun River Basin. Arab. J. Geosci. 2021, 14, 10.
10. Nadjai, S.; Bouderbala, A.; Khammar, H.; Nabed, A.N.; Benaabidate, L. Assessment of groundwater suitability for drinking and
irrigation purposes in the middle Cheliff Aquifer, Algeria. Desalination Water Treat. 2024, 319, 100528. [CrossRef]
11. Liu, W.; Jiang, S.J.; Chen, J.P.; Li, D.L.; Gao, Y.L.; Xing, J.F. A Brief Analysis on the Occurrence Regularity and Development and
Utilization of Fracture Water in Bedrock in Laixi City. Shandong Land Resour. 2021, 37, 28–34.
12. Liu, J.T.; Peng, Y.M.; Li, C.S.; Gao, Z.J.; Chen, S.J. An investigation into the hydrochemistry, quality and risk to human health of
groundwater in the central region of Shandong Province, North China. J. Clean. Prod. 2021, 282, 125416. [CrossRef]
13. Álvarez Torres, B.; Sotomayor Ramírez, D.R.; Castro Chacón, J.P.; Martínez Rodríguez, G.; Pérez Alegría, L.R.; DeSutter, T.M.
An alternative method to measure electrical conductivity (EC) and sodium adsorption ratio (SAR) in salt-affected soil extracts.
Front. Environ. Sci. 2023, 11, 1108272. [CrossRef]
14. Ramesh, B.K.; Pillai, M.V.; Vanitha, S.; Diagu, J. Analysis of surface water quality for irrigation in Padmanabhapuram fort
(Kanyakumari District, Tamil Nadu) India. IOP Conf. Ser. Mater. Sci. Eng. 2020, 872, 012191. [CrossRef]
15. Murray, G.E. Midway Stage, Sabine Stage, and Wilcox Group. AAPG Bull. 1955, 39, 671–696.
16. Thorne, D.W. Diagnosis and Improvement of Saline and Alkali Soils. Agron. J. 1954, 46, 290. [CrossRef]
17. Merouche, A.; Selvam, S.; Imessaoudene, Y.; Maten, C.N. Assessment of dam water quality for irrigation in the northeast of
catchment Cheliff-Zahrez, Central Algeria. Environ. Dev. Sustain. 2019, 22, 1–22. [CrossRef]
Water 2025, 17, 276 16 of 17

18. Siddhant, D.; Kalamdhad, A.S. Hydrochemical dynamics of water quality for irrigation use and introducing a new water quality
index incorporating multivariate statistics. Environ. Earth Sci. 2021, 80, 73.
19. Simler, R. Diagrammes Software; Avignon University: Avignon, France, 2009.
20. Vystavna, Y.; Schmidt, S.; Diadin, D.; Rossi, P.M.; Vergeles, Y.; Erostate, M.; Vadillo, I. Multi-tracing of recharge seasonality and
contamination in groundwater: A tool for urban water resource management. Water Res. 2019, 161, 413–422. [CrossRef] [PubMed]
21. Wang, L.; Mei, Y.; Yu, K.; Li, Y.; Meng, X.; Hu, F. Anthropogenic Effects on Hydrogeochemical Characterization of the Shallow
Groundwater in an Arid Irrigated Plain in Northwestern China. Water 2019, 11, 2247. [CrossRef]
22. Torres-Martínez, A.J.; Mora, A.; Mahlknecht, J.; Daesslé, L.W.; Cervantes-Avilés, P.A.; Ledesma-Ruiz, R. Estimation of nitrate
pollution sources and transformations in groundwater of an intensive livestock-agricultural area (Comarca Lagunera), combining
major ions, stable isotopes and MixSIAR model. Environ. Pollut. 2020, 269, 115445. [CrossRef]
23. Gao, Z.J.; Chen, C. The classification method of water chemical types based on the principle of Kurllov’s formula and Shoka Lev
classification. Groundwater 2018, 40, 6–13.
24. Piper, A.M. A graphic procedure in the geochemical interpreation of water-analyses. EOS Trans. Am. Geophys. Union 1944, 25,
27–29.
25. Gao, Z.J.; Wang, Z.Y.; Wang, S.; Wu, X.; An, Y.H.; Wang, W.X.; Liu, J.T. Factors that influence the chemical composition and
evolution of shallow groundwater in an arid region: A case study from the middle reaches of the Heihe River, China. Environ.
Earth Sci. 2019, 78, 390. [CrossRef]
26. Gibbs, A.J.; McIntyre, G.A. The Diagram, a Method for Comparing Sequences. Eur. J. Biochem. 1970, 16, 1–11. [CrossRef]
[PubMed]
27. Rajput, U.; Swami, D.; Joshi, N. Geospatial analysis of toxic metal contamination in groundwater and associated health risks in
the lower Himalayan industrial region. Sci. Total Environ. 2024, 938, 173328. [CrossRef] [PubMed]
28. Luo, Y.F.; Xiao, Y.; Hao, Q.C.; Zhang, Y.H.; Zhao, Z.; Wang, S.B.; Dong, G.F. Groundwater geochemical signatures and implication
for sustainable development in a typical endorheic watershed on Tibetan plateau. Environ. Sci. Pollut. Res. Int. 2021, 28,
48312–48329. [CrossRef] [PubMed]
29. Jiang, W.Q.; Li, B.Z.; Zhang, Z.; Zhang, Y. Hydrochemical Characteristics, Controlling Factors and Groundwater Sources of
Zaozigou Gold Mine. Sustainability 2024, 16, 7989. [CrossRef]
30. Li, P.; Wu, J.; Qian, H. Hydrochemical appraisal of groundwater quality for drinking and irrigation purposes and the major
influencing factors: A case study in and around Hua County, China. Arab. J. Geosci. 2015, 9, 15. [CrossRef]
31. Han, C.; Liu, J.T.; Gao, Z.J.; Xu, Y.; Zhang, Y.Q.; Han, Z.; Zhao, Z.H.; Luo, Z.J. Chemical characteristics, evolution, and quality
of groundwater and processes controlling its fluoride concentration features: Case study of a typical high-fluoride areas in the
Southwestern Shandong Plain, China. Environ. Sci. Pollut. Res. Int. 2022, 29, 19003–19018. [CrossRef] [PubMed]
32. Vetrimurugan, E.; Rajmohan, N.; Bongani, S.; Li, P.Y.; Sivakumar, U.; Johan, V.T. Geochemical evolution and the processes
controlling groundwater chemistry using ionic ratios, geochemical modelling and chemometric analysis in a semi-arid region of
South Africa. Chemosphere 2022, 312, 137179.
33. Yang, Q.; Li, Z.; Ma, H.; Wang, L.; Martín, J.D. Identification of the hydrogeochemical processes and assessment of groundwater
quality using classic integrated geochemical methods in the Southeastern part of Ordos basin. China. Environ. Pollut. 2016, 218,
879–888. [CrossRef]
34. Nematollahi, M.J.; Ebrahimi, P.; Razmara, M.; Ghasemi, A. Hydrogeochemical investigations and groundwater quality assessment
of Torbat-Zaveh plain, Khorasan Razavi, Iran. Environ. Monit. Assess. 2015, 188, 2. [CrossRef]
35. Liu, J.T.; Gao, Z.J.; Zhang, Y.Q.; Sun, Z.B.; Sun, T.Z.; Fan, H.B.; Wu, B.; Li, M.B.; Qian, L.L. Hydrochemical evaluation of
groundwater quality and human health risk assessment of nitrate in the largest peninsula of China based on high-density
sampling: A case study of Weifang. J. Clean. Prod. 2021, 322, 129164. [CrossRef]
36. Liu, J.T.; Gao, Z.J.; Wang, Z.Y.; Xu, X.; Su, Q.; Wang, S.; Xing, T. Hydrogeochemical processes and suitability assessment of
groundwater in the Jiaodong Peninsula, China. Environ. Monit. Assess. 2020, 192, 384. [CrossRef] [PubMed]
37. Xiao, J.; Zhang, F.; Jin, Z. Spatial characteristics and controlling factors of chemical weathering of loess in the dry season in the
middle Loess Plateau, China. Hydrol. Process. 2016, 30, 4855–4869. [CrossRef]
38. Fan, B.; Zhao, Z.; Tao, F.; Liu, B.; Tao, Z.; Gao, S.; Zhang, L. Characteristics of carbonate, evaporite and silicate weathering
in Huanghe River basin: A comparison among the upstream, midstream and downstream. Asian Earth Sci. 2014, 96, 17–26.
[CrossRef]
39. Wu, C.; Wu, X.; Qian, C.; Zhu, G. Hydrogeochemistry and groundwater quality assessment of high fluoride levels in the Yanchi
endorheic region, northwest China. Appl. Geochem. 2018, 98, 404–417. [CrossRef]
40. Li, C.S.; Gao, Z.J.; Chen, H.L.; Wang, J.X.; Liu, J.T.; Li, C.; Xu, C. Hydrochemical analysis and quality assessment of groundwater
in southeast North China Plain using hydrochemical, entropy-weight water quality index, and GIS techniques. Environ. Earth Sci.
2021, 80, 523. [CrossRef]
Water 2025, 17, 276 17 of 17

41. Wang, M.R.; Zhang, Q.; Li, Y.A.; Bak, M.; Feng, S.; Kroeze, C. Water pollution and agriculture: Multi-pollutant perspectives. Front.
Agric. Sci. Eng. 2023, 10, 639–647. [CrossRef]
42. Maryna, S.; Zhaohai, B.; Wietse, F.; Nynke, H.; Albert, A.K.; Fulco, L.; Lin, M.; van Peter, P.; Emiel, S.J.; Vermeulen, L.C.; et al.
Urbanization: An increasing source of multiple pollutants to rivers in the 21st century. Npj Urban Sustain. 2021, 1, 24.
43. Pérez-Lucas, G.; Vela, N.; El Aatik, A.; Navarro, S. Environmental risk of groundwater pollution by pesticide leaching through
the soil profile. In Pesticides-Use and Misuse and Their Impact in the Environment; Larramendy, M., Soloneski, S., Eds.; Intech Open:
London, UK, 2019; pp. 1–28.
44. Kumar, M.; Goswami, R.; Patel, A.K.; Srivastava, M.; Das, N. Scenario., perspectives and mechanism of arsenic and fluoride
co-occurrence in the groundwater: A review. Chemosphere 2020, 249, 12612623. [CrossRef] [PubMed]
45. Wang, W.; Zhang, D.; Kong, H.; Zhang, G.; Shen, F.; Huang, Z. Effects of Salinity Accumulation on Physical, Chemical, and
Microbial Properties of Soil under Rural Domestic Sewage Irrigation. Agronomy 2024, 14, 514. [CrossRef]

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