Science of the Total Environment 607–608 (2017) 586–599

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Science of the Total Environment

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Evolutionary process of saline-water intrusion in Holocene and Late

Pleistocene groundwater in southern Laizhou Bay
Sen Liu a,c,d, Zhonghua Tang a, Maosheng Gao b,c,⁎, Guohua Hou b,c
a
School of Environmental Studies, China University of Geosciences, 388 Lumo Rd, Wuhan, 430074, China
b
Laboratory for Marine Geology, Qingdao National Laboratory for Marine Science and Technology, Qingdao, 266061, China
c
Qingdao Institute of Marine Geology, CGS, Qingdao 266071, China
d
Chinese Academy of Geological Sciences, Beijing 100037, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Structure of sedimentary layer is the

dominant controlling factor of ground-
water distribution.
• The salt of saline water (brine) is from
the dissolution of evaporates.
• Saline water intrusion presents wedge-
shaped intrusion pattern.
• Combined of HFE-D, there are differ-
ences of saline water intrusion process
between Holocene groundwater and
Late Pleistocene groundwater.

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

Article history: Saline water intrusion is one of the most serious groundwater problems in southern Laizhou Bay. In this study,
Received 19 April 2017 formation of groundwater with different qualities and saline water intrusion were analyzed using hydrochemical
Received in revised form 29 June 2017 and stable isotopic methods, and the Hydrochemical Facies Evolution Diagram (HFE-Diagram). The results dem-
Accepted 29 June 2017
onstrate that the structure of the sedimentary layer in this area is the dominant controlling factor of groundwater
Available online 27 July 2017
distribution. From the south (land) to the north (sea), the hydrochemical distribution presents a regular changing
Editor: Jay Gan pattern following the order: HCO3-Na·Mg and HCO3·Cl-Mg·Ca (fresh water), HCO3·Cl-Na·Mg (brackish water),
Cl-Na·Mg (saline water), Cl-Na (saline water) and Cl·HCO3-Na (brackish water). Hydrochemical data show that
Keywords: saline water and brine are not the result of evaporation or the concentration of seawater. Brackish water and sa-
Saline-water intrusion line water with low mineralization in Holocene groundwater are formed by the mixing of fresh water and highly
Hydrochemistry mineralized saline water, dissolution of evaporates by meteoric water, and water/salt interaction. And the saline
HFE-Diagram water formed through dissolution of evaporates in Holocene and Late Pleistocene groundwater. Isotopic results
Southern Laizhou Bay reveal that the main recharge of saline water in Holocene groundwater and Late Pleistocene groundwater is a
Evolutionary process
combination of the meteoric water and lateral recharge from rivers. Saline water intrusion was found to follow
a wedge-shaped intrusion pattern. Significant variations in Cl- and Na + indicate saline intrusion in the southern
area. The degree of saline water intrusion in Holocene groundwater was found to be more serious than that in
Late Pleistocene groundwater. Hydrochemical data and HFE-Diagram show that there is an intrusion process
in Holocene groundwater. In this process, it is accepted the fresh water recharge, such as meteoric water and lat-
eral recharge from rivers. In Late Pleistocene groundwater, it presents a simple intrusion process from saline
water to fresh water.
© 2017 Elsevier B.V. All rights reserved.

⁎ Corresponding author (Maosheng Gao) at: Qingdao Institute of Marine Geology, Fuzhounan Road NO. 62, Qingdao, Shandong Province, China.
E-mail addresses: luicent@sina.com (S. Liu), zhhtang@cug.edu.cn (Z. Tang), gmaosheng@cgs.cn (M. Gao), houguohua1987@163.com (G. Hou).

http://dx.doi.org/10.1016/j.scitotenv.2017.06.262
0048-9697/© 2017 Elsevier B.V. All rights reserved.
 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
1. Introduction
Residential coastal zones have the fastest growing economy and
most dense population in the world, increasing the local demands for
groundwater and pressure on the environment (Gao and Zhu, 2006;
Han et al., 2014). To meet the demands, groundwater resources have
been extensively exploited in coastal zones, which has led to a series
of environmental problems. Among several problems, seawater (saline
water) intrusion is the most prominent, and it leads to various other en-
vironmental issues, such as soil salinization and groundwater pollution
(salinization), which negatively affect agricultural production and cause
shortage of drinking water (Barker et al., 1998; Huang and Guo, 2008;
Barlow and Reichard, 2010; Li et al., 2011). Since the 1970s, some
groundwater depression cones have been forming because of excessive
groundwater (fresh water and brine) exploitation in southern Laizhou
Bay. This has induced a complex hydrodynamic field and caused the in-
trusion of saline water to fresh water aquifers, leading to fresh water sa-
linization (Zhang et al., 1997; Xue et al., 1997, 2000; Feng et al., 2006).
Furthermore, groundwater salinization involves evaporation condensa-
tion, hydrolysis, dissolution of evaporated salts and the mixing of
groundwater of different qualities and hydrochemistry (Matthess,
1982; Drever, 1997; Clark and Fritz, 1997; Mazor, 2004; Applo and
Postma, 2005; Edmunds et al., 2006; Ma et al., 2007; Gu, 2011; Salama
et al., 1999; Yang et al., 2016a, 2016b; Todd and Mays, 2005).
Southern Laizhou Bay has a wide distribution and high concentra-
tion of brine, and is one of the main brine storage areas in China
(Zheng et al., 2014). The unique meteorological and hydrological condi-
tions as well as ancient geographical environment and topographic fea-
tures of southern Laizhou Bay provide suitable conditions for the
formation of local brine (Gao et al., 2015, 2016). Stable isotopic and
hydrochemical analyses have revealed that the salt in brine (saline
water) formed by evaporation of seawater left behind during transgres-
sion and regression in the Late Pleistocene and Holocene. Subsequent
supply of moisture through precipitation, recharge from piedmont
groundwater, and lateral recharge from rivers resulted in the saline
water (Han et al., 2011, 2014; Yang et al., 2016a, 2016b).
Underground saline water in southern Laizhou Bay has formed
under the background of transgression and regression during Late Pleis-
tocene and Holocene, and its salinity is higher than that of seawater
(Gao et al., 2015, 2016). This study was conducted to investigate the
evolutionary process of saline water intrusion of Late Pleistocene and
Holocene groundwater. For this purpose, groundwater monitoring
wells of different depths were set and groundwater samples were col-
lected to obtain basic data for analysis and discussion. Stable isotopic
and hydrochemical methods were employed to analyze the origin of
moisture and salt of groundwater. Furthermore, the Hydrochemical Fa-
cies Evolution Diagram (HFE-Diagram) was used in discussing the
mixing process and mechanism of saline water intrusion in different
aquifers of Holocene and Late Pleistocene sedimentary strata (80 m
depth above) (Edmunds, 1996; Edmunds et al., 2006; Hiroshiro et al.,
2006; Gates et al., 2008; Schiavo et al., 2009; Giménez-Forcada, 2010,
2014).
2. Background of study area
2.1. Location and climatic conditions
The study area is located north of Shandong Peninsula and southern
Laizhou Bay, Bohai Sea, China (Fig.1 (a)). The slope of the terrain is gentle
and flattens gradually from south (land) to north (sea). The study area
also lies in the downstream basin of Bailanghe River, where saline
water is widely distributed and saline intrusion is more serious. Bailanghe
River is 127 km long with an average flow rate of 3.88 × 107 m3/a, and is
the one of the main recharge resource of shallow groundwater within the
study area. One half of the study area belongs to the warm temperate
zone, and the other half to the moist monsoon climatic region. The
587
mean annual temperature is 53.9 °F, and the average annual precipitation
is 731 mm. Most of the total annual precipitation, 70%–80% occurs during
July–September. The mean annual evaporation capacity is 1648 mm, with
50% of the total evaporation capacity attributed to the months from
March to June (Bi et al., 2012; Han et al., 2014; Gao et al., 2015; Liu
et al., 2016).
2.2. Geology
According to previous research, on the sedimentary strata of this
area, several transgression layers and saline water sedimentations
formed in the Early and Middle Pleistocene in the study area (Gao
et al., 2015). Since the Late Pleistocene, the study area has experienced
many glacial–interglacial climatic alternations. In particular, three obvi-
ous temperature fluctuations occurred, namely from 85 to 76 ka BP, 50
to 24 ka BP, and 10 to 4 ka BP. These three periods were accompanied by
three transgressions (Cangzhou transgression, Xianxian transgression,
and Huanghua transgression), known as the marine–continental transi-
tion depositional environment (Fig. 1(a)). Between these periods, two
cold dry periods (Early Dali ice period and the Late Dali ice period) oc-
curred from 76 to 50 ka BP, and from 24 to 10 ka BP, providing a conti-
nental sedimentary environment (Qin, 1985; Zhuang et al., 1987; Zhang
et al., 2005). The marine–continental transition sedimentary strata
formed as a result of transgression and regression. From top to bottom,
the sedimentary layers are as follows: the Late Holocene continental
layer, Holocene Huanghua transgression layer, Early Holocene conti-
nental layer, Late Pleistocene glacial continental layer, Xianxian trans-
gression layer from the later part of the Late Pleistocene, continental
layer from the later part of the Late Pleistocene and Early glacial age,
and Cangzhou transgression layer from the early part of the Late Pleisto-
cene (Qin, 1985).
Overall, three massive sea level fluctuations occurred and three ma-
rine sedimentary strata formed: the first, second and third marine sed-
imentary strata. Masses of seawater collected in these marine
sedimentary strata and were occupied by continental deposits formed
during regression. The amount of silt in continental deposits was corre-
spondingly increased, along with the weakening of the river carrying
capacity in the marine zone. This served the role of closing or closed cov-
ering on marine sedimentary layers (Gao et al., 2015, 2016).
2.3. Hydrological conditions
Fresh water, brackish water, saline water and brine aquifers are dis-
tributed throughout the study area (Fig. 1(c)) (Han et al., 2014; Liu et al.,
2016). The shallow freshwater aquifers mainly comprise fine sand and
medium fine sand. The shallow fresh water contains Cl·HCO3·SO4-
Ca·Na, Cl-Ca·Na, HCO3-Ca·Na, and HCO3·SO4·Cl-Na (Bi et al., 2012)
and the value of total dissolved solids (TDS) is b1 g/L. Brackish water
and saline water aquifers mainly comprise silty sand, fine sand, clay
silt, and their TDS values range from 1 to 50 g/L. Brine aquifers are com-
posed of phreatic to confined aquifers (1st Marine brine layer, TDS =
50–130 g/L), the first and the second brine aquifers (2nd Marine brine
layer, TDS = 50–165 g/L), and the third and fourth brine aquifers (3rd
Marine brine layer, TDS = 50–140 g/L) (Qin, 1985; Zheng et al., 2014;
Gao et al., 2015).
The study area features an ancient buried channel with coarse sedi-
ments, allowing ample groundwater movement (Liu et al., 2003). Under
natural conditions, the flow direction of groundwater is from south
(piedmont area) to north (sea area). The shallow groundwater is mainly
recharged by meteoric water and lateral recharge of rivers, and it is
discharged mainly through atmospheric evaporation and groundwater
exploitation. In contrast, the recharge source of deep groundwater aqui-
fers is groundwater from other aquifers. Nevertheless, they are
discharged mainly through artificial exploitation. Near the coastal line,
groundwater is influenced by tides and waves, but their influence is lim-
ited within the context of this study, and thus they were not considered.
588 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599

Fig. 1. (a) and (b): Location of the study area and the line of transgression (early Late Pleistocene, late Late Pleistocene and Holocene), location of the monitoring wells and groundwater
sampling site (Modified from Liu et al., 2016 and Han et al., 2014). (ZK06: ZK06-30, ZK06-80; ZK04: ZK04; ZK09: ZK09-30, ZK09-80; ZK03: ZK03-30, ZK03-80; ZK08: ZK08; ZK05: ZK05;
ZK07: ZK07-30, ZK07-80). (c): Geological section showing the distribution of groundwater quality and flow directions from hydrological data and the location of groundwater sampling site
and monitoring wells. The hydrogeological profile is based on geological and hydrological data from past research and monitoring data (Modified from Liu et al., 2016 and Han et al., 2014).
 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
Since the 1970s, the demands for water for agriculture and ani-
mal husbandry have been increasing in the study area. To meet the
demands, artificial exploitation of groundwater has been excessively
employed. Consequently, a number of groundwater depression
zones have formed mainly in the southern fresh water and northern
brine areas. Depression zones play a significant role in changing the
direction of local groundwater flow (Han et al., 2014). Previous stud-
ies reported that the total precipitation in the study area is small and
stream cutoff of river has become more serious in recent years. A
complex groundwater dynamic field has formed and led to the flow
of saline water to fresh water areas. Consequently, the issue of saline
water intrusion is gradually becoming more serious (Feng et al.,
2006; Liu et al., 2004).
3. Materials and methods
3.1. Groundwater monitoring
Shallow fresh water, shallow saline water, deep fresh water,
deep saline water and deep brine aquifers are distributed in the
study area (Fig. 1(c)). Based on the local sedimentary strata, distri-
bution of groundwater, and hydrogeological conditions, the aqui-
fers were divided into two types for analysis and discussion:
aquifers in the Holocene strata (hereinafter referred to as “Holocene
groundwater”) at a depth of 25 m, including unconfined aquifers,
micro confined aquifer and confined aquifers; aquifers in the Late
Pleistocene strata (hereinafter referred to as “Late Pleistocene
groundwater”) at a depth of 25–80 m, including confined aquifers
(Liu et al., 2016).
Based on the geological background and distribution characteristics
of groundwater quality in the study area, 9 monitoring wells (Table 1,
Fig. 1(c)) were set up and 30 groundwater samples (Table S1,
Table S2, Fig. 1(c)) were collected to monitor the dynamic changes in
groundwater level and the distribution of groundwater quality. For Ho-
locene groundwater, six wells were set from south (land) to north
(sea): ZK06-30, ZK04, ZK09-30, ZK03-30, ZK08, and ZK07-30
(Table 1). The remaining three were set along the same direction to
monitor Late Pleistocene groundwater: ZK09-80, ZK05, and ZK07-80
(Table 1). For comparison, 1 seawater sample, 1 local rain sample and
2 water samples of Bailanghe River were collected simultaneously
(Table S1, Table S2).
To determine the distribution of groundwater, groundwater sam-
ples were collected at different depths (Fig. 1(c)) using the fixed-
depth sampling equipment (FFS-A type) developed by the Center
for Hydrogeology and Environmental Geology of the Chinese Geo-
logical Survey. This equipment works on the principle of the balance
between the water pressure and atmospheric pressure, and it can
guarantee the quantity of water samples obtained from different
aquifers.
3.2. Analytical methods
Two monitoring methods were applied: dynamic changes of
groundwater level monitoring method and continuous longitudinal
monitoring method. CTD-Diver (Netherlands) was used to monitor
groundwater for the following periods: normal season (Oct–Jan), dry
season (Feb–Jun), and wet season (Jul–Sep). The monitoring equipment
were calibrated and adjusted before installation and every 2 months to
ensure the reliability of the data. Groundwater quality is expressed in
terms of electrical conductivity (EC, unit: mS/cm). Groundwater level
is determined from groundwater pressure (unit: cm H2O) and calculat-
ed using the following formula:
 
P−P0
H ¼ H0 − h−
100
589
where H is groundwater level (m), H′ is ground elevation (m), h is the
depth at which CTD-Diver is installed (m), P is instrument monitoring
pressure (cm H2O), and P′ is atmospheric pressure of monitoring
wells (cm H2O).
Stable isotopes (δ18O, δ2H) were measured at the Experimental &
Testing Center of Marine Geology, Ministry of Land and Resource,
China using High Temperature Pyrolysis-Isotope Ratio Mass Spectrom-
etry (HT-IRMS) (MAT253, Scientific Instrument Services, USA). Sodium
(Na+), potassium (K+), calcium (Ca2+), magnesium (Mg2+), chloride
(Cl−), sulfate (SO2− − 2−
4 ), bicarbonate (HCO3 ), carbonate (CO3 ), bromine
− −
(Br ), and iodine (I ) were determined through Atomic Absorption
Spectrometry (TAS-990, Beijing Purkinje General Instrument Co., Ltd.,
China), Ultraviolet Visible Spectrometry (TU-1901 Spectrophotometer,
Xi'An Yima Opto-Electrical Technology Co., Ltd., China) and Inductively
Coupled Plasma Atomic Emission Spectroscopy (Optima 2100 DV,
PerkinElmer Inc., USA) (Table S1, Table S2).
The Pearson correlation coefficients among the value of electrical
conductivity (EC), total dissolve solid (TDS), and each ion (Cl−, SO2−
4 ,
Na+, Ca2 +, Mg2 +) were calculated by the SPSS Statistics software
(IBM Corp., USA). Groundwater types were classified as follows: fresh
water (TDS b 1 g/L), brackish water (TDS = 1–3 g/L), saline water
(TDS = 3–50 g/L), and brine (TDS N 50 g/L) (Zhou, 2013). The
hydrochemical types of groundwater were set according to the classifi-
cation method proposed by S. Shukalov, in which the percentage of the
mEq that is N 25% of the group score is ranked according to its contents
(Wang et al., 2006).
4. Results and discussions
4.1. Dynamic changes in groundwater level
Monitoring data revealed the formation of two clear groundwater
depression zones in ZK04 (Gudi) and ZK05 (north of Yangzi). The low-
est groundwater levels were − 8.776 m in ZK04 and − 44.601 m in
ZK05 (Fig. 1(c), Fig. 2, Table 2.). The main reason for these depressions
is the excessive groundwater exploitation (fresh water exploitation
around ZK04 and brine exploitation around ZK05).
4.1.1. Holocene groundwater
In the normal season, the groundwater levels of ZK04, ZK09-30,
ZK03-30, and ZK07-30 remained unchanged over the observation peri-
od and showed a steady state. The groundwater level of ZK06-30
showed a fluctuation trend but did not change significantly on the
whole. However, in the dry season, groundwater levels of ZK09-30
showed a gradual decreasing trend, because the amount of recharge
was lower than the amount of exploitation. In wells of ZK03-30 and
ZK08, groundwater levels presented a clear fluctuation trend. This indi-
cates the existence of supply sources along with groundwater exploita-
tion, such as rainfall and lateral recharge of river. In the wet season,
groundwater levels showed a clear increasing trend under the influence
of meteoric water (Fig. 2).
4.1.2. Late Pleistocene groundwater
In the normal season, groundwater levels of ZK09-80 and ZK07-80
were stable and that of ZK05 (brine monitoring well) showed an in-
creasing trend. In the dry season, groundwater levels decreased signifi-
cantly because of groundwater exploitation. Groundwater in ZK07-80
remained stable because it lies far from residential areas and is not influ-
enced by human activities. In the wet season, groundwater levels
showed a clear increasing trend with increases in rainfall. The buried
depth of Late Pleistocene groundwater is deeper, and the effect of rain-
fall is smaller. Therefore, increases in groundwater levels are lower than
those of Holocene groundwater (Fig. 2).
In summary, groundwater levels show seasonal change characteris-
tics which are determined by meteoric water and artificial groundwater
exploitation. Two large-scale groundwater depression zones have
590 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599

Table 1
The data of monitoring wells.

Groundwater Number of monitoring wells Coordinate Depth (m) Types of groundwater

Longitude Latitude

Holocene groundwater ZK06-30 119°09′20.33″ 36°50′41.95″ 30 Fresh water

ZK04 119°08′54.84″ 36°52′07.67″ 80 Brackish water
ZK09-30 119°08′57.20″ 36°53′54.27″ 30 Saline water
ZK03-30 119°10′21.94″ 36°56′15.78″ 30 Saline water
ZK08 119°10′52.64″ 36°57′58.44″ 30 Saline water
ZK07-30 119°12′26.71″ 37°13′10.41″ 30 Saline water
Late Pleistocene groundwater ZK09-80 119°08′57.20″ 36°53′54.27″ 80 Saline water
ZK05 119°08′42.24″ 37°06′33.76″ 80 Brine
ZK07-80 119°12′26.71″ 37°13′10.44″ 80 Saline water

formed due to groundwater exploitation. Holocene groundwater is season. Compared to Holocene groundwater, the depth of Late Pleisto-
mainly influenced by groundwater exploitation in the dry season, and cene groundwater is deeper and the effect of rainfall is smaller, and
by meteoric water and groundwater artificial exploitation in the wet therefore, it is primarily affected by groundwater exploitation. The

Fig. 2. Groundwater level fluctuation and range of Holocene groundwater and Late Pleistocene groundwater.
 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
Table 2
Groundwater level fluctuation ranges of Holocene groundwater and Late Pleistocene groundwater.
Groundwater Number of monitoring wells
Holocene groundwater ZK06-30
ZK04
ZK09-30
ZK03-30
ZK08
ZK07-30
Late Pleistocene groundwater ZK09-80
ZK05
ZK07-80
complex groundwater dynamic field has induced a change in the flow
direction of groundwater and eventually led to the mixing of groundwa-
ter of different qualities.
4.2. Water quality distribution and area of saline water intrusion
4.2.1. Relationships among EC, TDS, and Cl−
Electric conductivity (EC) is a physical index that can reflect the
quality of groundwater. According to calculations using the SPSS Statis-
tics software, there is an obviously positive linear correlation among
EC values, TDS values and Cl− concentrations (EC values and TDS values,
R2 = 0.983, Pearson correlation coefficient = 0.991; EC values and Cl−
concentrations, R2 = 0.978, Pearson correlation coefficient = 0.989)
(Fig. 3). This means that the higher the EC values are, the higher the
TDS values and Cl− concentrations are. The quality distribution of
local groundwater can be determined using monitored EC values.
4.2.2. Continuous longitudinal EC monitoring data
The results show that the distribution pattern of EC is “low–high–
low” from south (land) to north (sea) at the same groundwater level.
In the southern fresh water zone (ZK06), the EC value gradually in-
creased from 0.85 mS/cm to 0.95 mS/cm. It showed a weak increasing
trend but the groundwater quality maintained the fresh water state.
In the ZK04 (brackish water) and ZK09 (saline water), the distribution
pattern of EC was “low–high–low”. Longitudinally, EC gradually in-
creased in ZK03 (7.86–96.29 mS/cm, increasing range of 88.43mS/cm),
ZK08 (7.38–31.56 mS/cm, increasing range of 24.18 mS/cm), and ZK07
(1.66–64.86 mS/cm, increasing range of 63.20 mS/cm) from the top to
bottom. In the ZK05 (brine water), EC was higher than 125.0 mS/cm
with an increase of b4.0 mS/cm (Fig. 4).
4.2.3. Saline water intrusion area
A complex hydrodynamic field has formed as a result of the ground-
water exploitation. Consequently, groundwater of different qualities
may get mixed and change the distribution characteristics. According
Fig. 3. Relationships between TDS value (mg/L), Cl− concentration (mg/L) and EC value (mS/cm).
591
Monitoring date The range of groundwater level (m)
Oct.2014–Sep.2015 0.631–2.110
Oct.2014–Sep.2015 −8.776–−5.812
Dec.2014–Sep.2015 −3.482–1.015
Oct.2014–Sep.2015 −3.443–3.280
Dec.2014–Sep.2015 −5.896–−4.398
Oct.2014–Sep.2015 0.833–1.953
Dec.2014–Sep.2015 −3.026–−0.484
Oct.2014–Sep.2015 −44.601–−37.180
Oct.2014–Sep.2015 0.349–1.213
to the distribution characteristics derived from continuous longitudinal
EC monitoring data (Fig. 4), the EC values of ZK04 and ZK09, which are
located in the groundwater depression zone, showed a distribution pat-
tern of “low–high–low”. This pattern is different from the “low–high”
pattern in other areas and is not consistent with the groundwater distri-
bution characteristics of the study area. Because of saline water flowing
into the groundwater depression zone, a mixing between saline water
and fresh water occurred, leading to mineralization of groundwater in-
creasing. The results show that the saline water intrusion occurs in a
− 10–− 25 m section of ZK04 and a − 10–− 40 m section of ZK09
(Fig. 4). The saline water intrusion presents a wedge-shaped model
and the intrusion area in the north is wider than that in the south. The
formation of the groundwater depression zone is the dominant control-
ling factor of saline water intrusion (Fig. 9).
4.3. Evolutionary process I: Origin of water and salt
4.3.1. δ2H and δ18O compositions
GMWL: δ2H = 8δ18O + 10. The local meteoric water line (LMWL:
δ H = 7.8δ18O + 6.3, n = 8, R2 = 0.78) is based on the δ18O and δ2H
2
values of the average monthly rainfall monitored from 1986 to
1990 at Yantai (data from the International Atomic Energy Agency/
World Meteorological Organization (IAEA/WMO, 2006).
The δ18O and δ2H values were relatively small. Nevertheless, obvious
variations could be observed in the δ18O (−8.67‰–−3.57‰) and δ2H
(−61.4‰–−22.6‰) values, which are distributed around the local me-
teorological water line and lower than that of the seawater sample. The
δ18O and δ2H values are relatively small. The δ18O and δ2H values of
fresh water in Late Pleistocene groundwater were smaller than that in
Holocene groundwater. These values of fresh water in Holocene
groundwater are close to that of local meteorological water. The δ18O
and δ2H values of brackish water are located on the local meteorological
line. From the south (land) to the north (sea), δ18O and δ2H values of
groundwater samples tended to increase and approached the value of
592 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599

Fig. 4. Continuous longitudinal EC monitoring data of ZK06, ZK04, ZK09, ZK03, ZK08, ZK05, and ZK07 stations (monitoring data is of Jul. 21, 2016).
 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
seawater. Therefore, at the coastal line, groundwater is more signifi-
cantly influenced by seawater (Fig. 5(a)).
4.3.2. Groundwater recharge
The stable isotopic data showed that saline water and brine are not
the residues of seawater evaporation because the δ18O and δ2H values
in saline water and brine are lower than that in standard seawater
(δ18O and δ2H value are 0‰) and the local seawater sample (Horita,
2005). Along the local precipitation line, the δ18O and δ2H values indi-
cate that groundwater in the study area is mainly derived from the
local meteoric water. The δ18O and δ2H of saline water in Late Pleisto-
cene groundwater were more concentrated than that in Holocene
groundwater. Most values were distributed below the local meteorolog-
ical water line. The δ18O and δ2H values of saline water in Holocene
groundwater increase with increasing Cl− concentration. Because the
depth of Holocene groundwater is relatively shallower, it is significantly
influenced by persistent meteoric water and river water. The saline
water of Late Pleistocene groundwater received meteoric water replen-
ishment during its formation. However, with changes in the deposition-
al environment and the formation of the enclosed environment, it
stopped receiving recharge.
4.3.3. Hydrochemical characteristics
4.3.3.1. Hydrochemistry and major ions
4.3.3.1.1. Holocene groundwater. From the south (land) to the north
(sea), different hydrochemical types are distributed: HCO3-Na·Mg and
HCO3·Cl-Mg·Ca (fresh water), HCO3·Cl-Na·Mg (brackish water), Cl-
Na·Mg (saline water), Cl-Na (saline water), and Cl·HCO3-Na (brackish
water). HCO–3 is the main anion while Na+ and Mg2+ are the main cat-
ions in fresh water and brackish water samples. Cl− and Na+ are the
main ions whose milligram equivalent (mEq) percentages were up to
69.0% and 59.0% in saline water samples. Na+ mEq percentages of Holo-
cene groundwater samples were lower than that of the local sea sample
(93.5%). The mEq percentages of Cl−+SO2− were close to those of the
4
local seawater sample (99.7%) (Fig. 6(a)).
4.3.3.1.2. Late Pleistocene groundwater. The hydrochemical types var-
ied from the south (land) to the north (sea), such as HCO3-Na·Mg (fresh
water), HCO3·Cl-Na·Mg (brackish water), Cl-Na·Mg (saline water),
and Cl-Na (saline water and brine). Cl− (mEq percentage N 80%) and
Na+ (mEq percentage N 60%) are the main ions in saline water samples,
and the values of both are lower than those of the local seawater sample.
The mEq percentages of Cl−+SO2− 4 (98.3%–99.8%) of saline water sam-
ples were close to those of the local seawater sample (Fig. 6(a)).
Cl− concentrations of fresh water samples were 45.00–118.00 mg/L,
and those of brackish water samples were 190–300 mg/L. The Cl− con-
centration of fresh water and brackish water in Holocene groundwater
was higher than that in Late Pleistocene groundwater. Cl− concentra-
tions of saline water samples in Holocene groundwater were
2.00–16.70 g/L and less than that of the seawater sample (17.88 g/L).
Cl− concentrations of saline water samples of Late Pleistocene ground-
water were 2.00–25.00 g/L. At the same location (saline water area), Cl−
concentration in Late Pleistocene groundwater was higher than that in
Holocene groundwater. The Cl− concentration of brine sample was
higher than 60.00 g/L (Table S1).
In the study area, obvious differences were found between the mEq
percentages of saline water (brine) and the local seawater samples. This
indicates that the groundwater did not form through simple evapora-
tion and concentration of seawater. The process of formation involves
an external supply source or the occurrence of water/salt interaction.
At the same location (fresh water and brackish water areas), the Cl−
concentration of Holocene groundwater was higher than that of Late
Pleistocene groundwater, implying that Holocene groundwater is
more influenced by saline water intrusion.
593
4.3.3.2. Relationships among ions. The Na+/Cl− values of saline water
ranged 0.687–0.897, which is close to that of the local seawater sample
(0.827). The magnitudes of Na+/Cl− values of fresh water and brackish
water samples were larger, with values ranging 0.830–4.215. The
Mg2+/Cl− and Ca2+/Cl− values of saline water samples in Late Pleisto-
cene groundwater were higher than the value of the local seawater
sample (0.278, 0.038). Values of SO24 −/Cl− were close to the value of
the local seawater sample (0.104). The Mg2 +/Cl−, Ca2 +/Cl− and
SO2− −
4 /Cl values of water samples collected from near the coastal line
were close to the value of the local seawater sample. The Mg2 +/Cl−
value (0.209) and Ca2 +/Cl− value (0.010) of brine were lower than
that of the local seawater sample. And the value of SO2− −
4 /Cl (0.104)
was close to that of the local seawater sample.
4.3.3.3. Cl/Br and Cl−. Groundwater of different qualities is distributed in
study area. The sources of salt in brackish water, saline water and brine
are also different, such as sea water intrusion, evaporation and concen-
tration of ancient seawater in marine sedimentary layers, and water-salt
interaction (Zhang et al., 1997). The Cl/Br molar ratio has been used to
determine the source of salt in groundwater (TDS N 2–3 g/L) (Alcalá
and Custodio, 2008; Edmunds et al., 2006). The Cl/Br for seawater is
generally around 655 (Cl− = 550 mmol/L, Br− = 0.84 mmol/L,
Siemann, 2003), and the Cl/Br of the Laizhou Bay was 686.17 (Cl− =
503.72 mmol/L, Br− = 0.73 mmol/L, Table S1, Table S2, and Fig.7).
The Cl/Br ratio was large in groundwater samples with low mineral-
ization (Cl− b 8.5 mmol), ranging 90.33–2310.19 (Fig. 7). The Cl− con-
centration of saline water samples ranged 60.00–626.00 mmol and the
value of Cl/Br was 620.33–796.81 which is distributed under the line
of the local seawater sample, except for S150731 (Table S1, Table S2).
The Cl/Br value of brine reached up to 1023.29, which is clearly higher
than that of the local seawater sample.
4.3.4. Origin of salt
The results of this study showed that the mEq percentage of saline
water and brine samples are different from that of the local seawater
sample. Therefore, saline water and brine may not have formed from
the simple evaporation and concentration of seawater. It may have
other origins, such as other supply sources and a certain degree of
water/salt interaction.
Previous studies conducted evaporation experiments (Usiglio, 1849;
Yang et al., 2016b) and determined a Cl− concentration of seawater of
194,000 mg/L when 90% water in sea water evaporated. In those stud-
ies, NaCl did not precipitate out and Cl/Br ratio remained the same
with seawater (686.17). The Cl/Br ratio may be used as an indicator of
the origin of salinity, with values equal to or below the marine ratio like-
ly to originate from marine water or marine formation waters; values
much higher than the marine ratio indicate an evaporate source
(Edmunds, 1996). The Cl− concentrations of groundwater samples
were 45.00–60,407.86 mg/L and lower than 194,000 mg/L, which
means NaCl precipitation did not occur. If the saline water and brine
are products of evaporation and concentration of seawater, its Cl/Br
values should remain the same. The Cl/Br values of saline water and
brine were higher than that of local seawater, indicating that the saline
water and brine are not products of evaporation and concentration of
seawater, and the salt mostly originates from the dissolution of evapo-
rates. The Cl/Br values of fresh water and brackish water were large
and different from those of seawater sample (Fig. 7), indicating no di-
rect relationship between brackish water and seawater. Therefore,
brackish water may be the result of saline water intrusion and dissolu-
tion of evaporates.
The relationships between Na+, Mg2 +, SO24 −, Ca2 +, and Cl− are
shown in Fig.8. Logarithmic coordinates were used for analysis and
the unit is meq/L. The Pearson correlation coefficients between
Na+ and Cl−, between Mg2 + and Cl−, and between SO24 − and Cl−
of fresh water and brackish water in Holocene groundwater are
0.798, 0.076, and 0.802 (N = 0.105, 0.903, and 0.102), respectively.
594 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599

Fig. 5. Stable isotope composition of groundwater in the study area: (a): δ18O versus δ2H plot for groundwater, (b): δ18O versus Cl− in groundwater.

Na+ and Cl− as well as SO24 − and Cl− show strong positive correla-
tions. On the contrary, there is no correlation between Mg 2 + and
Cl−. Compared to Holocene groundwater, there is an obviously pos-
itive correlation between Na+ and Cl−, between Mg2 + and Cl−, and
between SO 24 − and Cl− of fresh water and brackish water in Late
Pleistocene groundwater, and the Pearson correlation coefficients
are 0.985, 0.991, and 0.971 (N = 0.105, 0.009, and 0.029), respective-
ly. It can be concluded that the salt of fresh water and brackish water
in Late Pleistocene groundwater originates from the dissolution of
evaporates, whereas the salt of fresh water and brackish water in Ho-
locene groundwater is from other sources (Gates et al., 2008;
Edmunds et al., 2006) (Fig. 7).
The Pearson correlation coefficients between Na+ and Cl−, between
Mg and Cl−, and between SO2−
2+ −
4 and Cl of saline water in Late Pleis-
tocene groundwater are 0.997, 0.957 and 0.858 (N = 0.000, 0.000, and
0.000), and those of saline water in Holocene groundwater are 0.997,
0.885, and 0.831 (N is 0.000, 0.002, and 0.006). On the whole, the results
show that there is a significantly positive correlation. This indicates that
the salt of saline water in Holocene groundwater and Late Pleistocene
groundwater originates from the dissolution of evaporates (Gates
et al., 2008; Edmunds et al., 2006; Yang et al., 2016a, 2016b) (Fig. 8).
In summary, the salt of fresh water, brackish water and saline water
located near the fresh water–saline water interface in Holocene ground-
water is from the intrusion of highly mineralized saline water and disso-
lution of evaporates by meteoric water and river lateral recharge. The
Cl/Br ratios of saline water and brine are higher than that of seawater,
indicating that salt in saline water and brine is mostly from the dissolu-
tion of evaporates. In Late Pleistocene groundwater, the salt of fresh
water, brackish water, and saline water are from the dissolution of evap-
orates. It is concluded that brine is not a product of the simple process of

Fig. 6. (a) Piper Diagram of various water samples. The red line shows water samples (fresh water and saline water) of Holocene groundwater in a different triangle. The blue line shows
water samples (fresh water and saline water) of Late Pleistocene groundwater in a different triangle. (b) Hydrochemical Facies Evolution Diagram (HFE-Diagram). 1: Na-HCO3, 2: Na-
MixHCO3, 3: Na-MixCl, 4: Na-Cl, 5: MixNa-HCO3, 6: MixNa-MixHCO3, 7: MixNa-MixCl, 8: MixNa-Cl, 9: MixCa·Mg-HCO3, 10: MixCa·Mg-MixHCO3, 11: MixCa·Mg-MixCl, 12:
MixCa·Mg-Cl, 13: Ca·Mg-Cl, 14: Ca·Mg-MixHCO3, 15: Ca·Mg-MixCl, 16: Ca·Mg-Cl.
 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
Fig. 7. Relationships between Br/Cl (mmol ratios) and Cl− (mmol/L).
evaporation and concentration. During this process, there are other
sources of salt. Based on the δ18O and δ2H values, meteoric water and
river lateral recharge are the main resource in the formation of brine.
After brine formation, the environment becomes closed and is not influ-
enced by other recharge resources.
4.4. Evolutionary process II: the mixing process
4.4.1. δ18O and Cl−
In the mixing process of atmospheric precipitation (fresh water) and
seawater (saline water), Cl− concentration increases with the δ18O
value of solvent increasing at a fixed proportion. Cl− concentration
and δ18O value have a positive correlation (Schiavo et al., 2009;
Hiroshiro et al., 2006).
In Holocene groundwater, δ18O values of fresh water and brackish
water were relatively large and range from − 8.67‰ to − 5.11‰
(Fig. 5(b)). δ18O values of brackish water showed an increasing trend
with increasing Cl− concentration, indicating that the brackish water
in Holocene groundwater is a mixture of saline water and meteoric
water (fresh water). However, the mixing process is not simple and in-
volves other functions. δ18O values of saline water ranged from −6.58‰
to −3.70‰ and Cl− concentration ranged 3.44–14.22 g/L. The Pearson
correlation coefficient between Cl− concentration and δ18O value is
0.533 (N = 0.140), indicating a weak positive correlation. It is conclud-
ed that saline water in Holocene groundwater is not only the product of
dissolution of evaporates by meteoric water but also the mixing of me-
teoric water (fresh water) and seawater (saline water) (Dakin et al.,
1983; Gat, 1996).
δ18O values of fresh water and brackish water in Late Pleistocene
groundwater were −8.56‰–−7.49‰. Without the influence of mete-
oric water, brackish water is formed by the mixing of fresh water and
saline water along with other functions. Compared to saline water in
595
Holocene groundwater, the distribution of δ18O values of saline water
in Late Pleistocene groundwater is more intensive. δ18O values were
−6.96‰–− 5.87‰ and Cl− concentrations were 11.61–22.24 g/L. The
Pearson correlation coefficient of Cl− concentration and δ18O value is
0.301 (N = 0.369), which indicates no correlation. Saline water samples
are not distributed on the mixing line of fresh water and brine samples
(Fig. 5(b)), which shows that it is not a product of mixing of fresh water
and brine but dissolution of evaporates by meteoric water (Dakin et al.,
1983; Gat, 2005). The Cl− concentration of brine sample was high while
the δ18O value was randomly distributed.
4.4.2. Hydrochemical Facies Evolution Diagram (HFE-Diagram)
Herein, the Hydrochemical Facies Evolution Diagram (HFE-Dia-
gram) is used to discuss the mixing process between fresh water and sa-
line water. The HFE-Diagram method enables easy identification of the
state of a coastal aquifer irrespective of intrusion/freshening phases that
take place over time and which are identified by the distribution of
anion and cation percentages in a square diagram (Giménez-Forcada,
2010, 2014). In the HFE-Diagram, three heteropic facies in Holocene
groundwater are identified: Na-Cl, saline water; Ca·Mg-MixHCO3,
brackish; Ca·Mg-HCO3, fresh water. Two heteropic facies are identified
in Late Pleistocene groundwater: Na-Cl, saline water; Na-HCO3
(Fig. 6(b)).
The HFE-Diagram shows that saline water (ZK09) in Holocene
groundwater is a result of mixing between saline water in ZK08 and
fresh water and presents an intrusion process. Brackish water samples
of Holocene groundwater are located in the freshening area. According
to analysis results, another recharge took place during the mixing pro-
cess between saline water and fresh water in the brackish water of Ho-
locene groundwater. In Late Pleistocene groundwater, it is a simple
intrusion process.
596 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599

4 , and Cl .
−
Fig. 8. Hydrochemical relationships between Na+, Mg2+, SO2−
 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
4.5. Evolutionary process III: Saline groundwater intrusion model
Since the Late Pleistocene, groundwater with different
hydrochemistry and water quality has formed in the study area. In the
southern area of the study site, fresh water is the main groundwater.
The main hydrochemistry is HCO3-Na·Mg. In the middle and northern
areas, saline water is predominant with a high degree of mineralization
and the main hydrochemistry comprises Cl-Na.
Without the intensive groundwater exploitation, groundwater
would flow from the south (piedmont area) to the north (sea area)
with a simple groundwater dynamic. The main cause of saline water in-
trusion would be groundwater dispersion, but it would not be signifi-
cant. However, groundwater exploitation has become more intensive
in recent years. Influenced by climate change and human activities
(constructions of river dam and reservoir), precipitation is decreasing
and the phenomenon of river cutoff is becoming more serious. Conse-
quently, many groundwater depression zones have emerged, leading
to a complex groundwater dynamic field in the study area. Overall, sa-
line water intrusion has become a serious issue. Fresh water in pied-
mont areas and saline water in the northern area flow to the
groundwater depression zone, which leads to the mixing of fresh
water and saline water. The distribution characteristics have been
Fig. 9. Distribution of groundwater hydrochemistry types, location of saline water intrusion and changes in the hydrochemistry in the saline water intrusion area.
597
changed in ZK04 and ZK09. Saline water intrusion presents a wedge-
shaped intrusion model. In the areas of saline water intrusion, Cl− and
Na+ concentrations increase significantly from fresh water, brackish
water to saline water. The hydrochemistry presents a transitional char-
acteristic of HCO3-Mg·Na (fresh water), HCO3·Cl-Na·Mg (brackish
water), Cl-Na·Mg (saline water), and Cl-Na (saline water) in proper
order from the south to the north. During intrusion, the mixing between
HCO3-Na·Mg groundwater (fresh water) south of ZK04 and Cl-Na·Mg
groundwater (saline water) north of ZK04 leads to increases in the
Cl− and Na+ concentration. The hydrochemical type changes to
HCO3·Cl-Na·Mg. Under the influence of northern Cl-Na groundwater
(saline water), Cl− and Na+ concentration keep increasing and the
hydrochemical type in ZK09 changes to Cl-Na·Mg (Fig.9).
The three-line graphical method can determine whether water is a
simple mixture of two types of water (Shen et al., 1990). Fig.6(a)
shows that the brackish water samples are not in the intersection of
the fresh water line and saline water line, indicating that it may not be
a simple mixture of fresh water and saline water. Clear differences
were found between Holocene groundwater and Late Pleistocene
groundwater. Combining the HFE-Diagram of Holocene groundwater
and Late Pleistocene groundwater, an intrusion process is found. In Ho-
locene groundwater, it presents an intrusion process in ZK09 and
598 S. Liu et al. / Science of the Total Environment 607–608 (2017) 586–599
freshening process in ZK04. Through the saline water intrusion process,
Holocene groundwater accepts the recharge from meteoric water and
lateral recharge from rivers. In general, it is an intrusion process. Be-
cause Late Pleistocene groundwater lies at a great depth, it can't be
recharged by meteoric water and lateral recharge from rivers. Subse-
quently, saline water intrusion is a simple intrusion process from saline
water to fresh water in Late Pleistocene groundwater. In addition, the
influence of saline water intrusion in Late Pleistocene groundwater is
less serious than that in Holocene groundwater from saline water to
fresh water.
5. Conclusions
Since the Late Pleistocene, southern Laizhou Bay has experienced
transgression and regression several times. In addition, storm surges
and other extreme weather events also occurred (Gao et al., 2015,
2016). A huge amount of seawater was retained in land, and its salinity
has been modified under the action of evaporation. Eventually, salt was
left behind in sediments, which became the provenance of saline water
and brine. Hydrochemical data reveal that salt in saline water and brine
is mostly from the dissolution of evaporates. Brackish water and saline
water with low mineralization were formed by the mixing of fresh
water and saline water with high mineralization, dissolution of evapo-
rates by meteoric water and water/salt interaction. In Late Pleistocene
groundwater, saline water is not a product of the mixing of fresh
water and saline water (brine), but rather a product of the dissolution
of evaporates. Isotopic results reveal that the main recharge of saline
water in Holocene groundwater and Late Pleistocene groundwater is
a combination of the meteoric water and lateral recharge from
rivers.
The distribution of groundwater is controlled by the structure of the
sedimentary layer. Due to excessive groundwater exploitation, depres-
sion zones have formed, and depression zones provide a leakage
through which highly mineralized groundwater can flow into brackish
water or fresh water aquifers. Saline water intrusion presents a
wedge-shaped intrusion model. Changes in hydrochemistry can fully
reflect saline water intrusion. In the transitional zone of fresh water
and saline water, significant changes in Cl− and Na+ concentration
can indicate the intrusion of highly mineralized groundwater (Cl-Na).
Hydrochemical data and HFE-Diagram show that there is an intrusion
process in Holocene groundwater. In this process, it is accepted the
fresh water recharge, such as meteoric water and lateral recharge
from rivers. In Late Pleistocene groundwater, it presents a simple intru-
sion process from saline water to fresh water. The degree of saline water
intrusion in Late Pleistocene groundwater is more serious than that in
Holocene groundwater.
At present, saline water intrusion has been effectively controlled to a
certain degree through relevant government policies and local ground-
water exploitation. Decreasing and unbalanced precipitation and the in-
tensive river cutoff decrease groundwater recharge, making saline
water intrusion more serious. The best measure to control saline
water intrusion is to enhance fresh water recharge in the intrusion
zone and maintaining groundwater exploitation at a reasonable level,
such as recovering stream discharge and building fresh water reservoirs.
Brine resource is becoming exhausted gradually owing to the unsus-
tainable and excessive brine exploitation in the recent years. During
brine exploitation, a part of the salt of brine may crystallize and attach
to the sediments. If brine exploitation is stopped, influenced by rainfall
and river side replenishment, the salt attached on the sediments will
be dissolved by fresh water. With prolonged replenishment, migration,
filtration and capping conditions, the mineralization of groundwater
will gradually increase. The brine resource can be generated again, but
the recovery period will be long. Decreases in the amount of recharge
(transgression, storm, etc.) can influence the quality of new brine
resources.
Acknowledgement
This research is financially supported by the National Key R&D Plan
of China (Grants No. 2016YFC0402801), the National Geological
Survey Project of China Geology Survey (Grants No. DD20160144),
and National Program on Key Basic Research Project of China (Grants
No. 2014FY210600). We thank Baojing Yue and Yunshui Jiang from
Qingdao Institute of Marine Geology and Fei Guo, for their help in pre-
paring this manuscript, collecting field data, and conducting geological
survey.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.scitotenv.2017.06.262.
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