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Spatial characteristics of water quality, stable isotopes and tritium

associated with groundwater flow in the Hutuo River alluvial fan


plain of the North China Plain
Yintao Lu & Changyuan Tang & Jianyao Chen &
Xianfang Song & Fadong Li & Yasuo Sakura

Abstract The groundwater flow system and the flow on the aquifer by causing excessive groundwater abstrac-
velocity in the alluvial fan plain of the Hutuo River, tion and irrigation return.
China, have been studied, with an emphasis on relating
geochemical characteristics and isotopes factors. Seven Résumé Le système d’écoulement de l’eau souterraine et la
stretches of one river, six springs and 31 wells, with vitesse d’écoulement dans le plaine du cône alluvial de la
depths ranging from 0 m (river waters) to 150 m, were Rivière Hutuo, Chine, ont été étudiés en mettant l’accent sur
surveyed. The groundwater has a vertical two-layer les caractéristiques géochimiques et les facteurs isotopiques
structure with a boundary at about 80–100 m depth, correspondants. Sept tronçons d’une rivière, six sources et
yielding an upper and a lower groundwater layer. The 31 puits, ayant des profondeurs allant de 0 m (eau de la
δ18O and δD values range from −10.56 to −7.05‰ and rivière) à 150 m, ont été examinés. L’eau souterraine a une
−81.83 to −59‰, respectively. The groundwater has been structure verticale à deux couches avec une limite à environ
recharged by precipitation, and has not been subjected to 80–100 m de profondeur, formant une couche supérieur
significant evaporation during infiltration into the aquifer d’eau souterraine et une inférieure. Les valeurs de ∂ 18 O et
in the upper layer. Using a tritium model, the groundwater de ∂ D vont de −10.56 à −7.05‰ et de −81.83 à −59‰,
flow in the alluvial fan plain showed horizontal flow respectivement. L’eau souterraine a été réalimentée par les
velocity to be greater than vertical velocity. Groundwater précipitations, et n’a pas été sujette à une évaporation
in the upper layer is characterized by Ca–HCO3 type. significative au cours de l’infiltration dans l’aquifère de la
From the spatial distribution characteristics of the stable couche supérieure. En utilisant modèle tritium, l’écoulement
isotope and chemical composition of the groundwater, de l’eau souterraine dans la plaine du cône alluvial a montré
agricultural irrigation was considered to have an influence une vitesse d’écoulement horizontal supérieure à la vitesse
verticale. L’eau souterraine de la couche supérieure est
caractérisée par un type Ca–HCO3. Du fait des caractéris-
tiques de la distribution spatiale en isotope stable et de la
Received: 15 May 2006 / Accepted: 17 February 2008 composition chimique de l’eau souterraine, l’irrigation
© Springer-Verlag 2008 agricole a été jugée avoir une influence sur l’aquifère en
occasionnant des prélèvements d’eau souterraine et une
restitution provenant de l’agriculture excessifs.
Y. Lu ()) : F. Li
Graduate School of Science and Technology, Resumen Se ha estudiado el sistema de flujo subterráneo y
Chiba University
Chiba 263–8522, Japan la velocidad de flujo en el cono aluvial del Río Hutuo, China,
e-mail: yintaolu2003@yahoo.co.jp enfatizando las características geoquímicas y su relación con
el contenido isotópico. Se relevaron siete tramos del río, seis
C. Tang
Faculty of Horticulture, Chiba University manantiales y 31 pozos, con profundidades que varían desde
Chiba 271–8510, Japan 0 m (agua del río) hasta 150 m. El complejo subterráneo
comprende dos capas con un límite a una profundidad
J. Chen
Zhongshan University aproximada de 80–100 m, constituyendo una capa subterrá-
Guangzhou 510275, China neas superior y una inferior. Los valores de δ18O yδD varían
entre −10.56 a −7.05‰ y −81.83 a −59‰, respectivamente.
X. Song
Institute of Geographic Sciences El agua subterránea se recargó por lluvias, y no ha estado
and Natural Resources Research sujeta a evaporación durante su infiltración en la capa
Beijing 100101, China superior del acuífero. El modelo de flujo subterráneo,
Y. Sakura
utilizando datos de tritio, mostró que la velocidad del flujo
Faculty of Science, Chiba University horizontal es mayor que la vertical. El agua subterránea de la
Chiba 263–8522, Japan capa superior es del tipo Ca–HCO3. Teniendo en cuenta la

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


distribución espacial de los isótopos estables y la compo- This is one of the most important areas for both
sición química del agua subterránea, se considera que el groundwater storage and human activity in China. Big
riego para agricultura ha tenido influencia en el acuífero cities with huge population, e.g. Beijing, Shijiazhuang and
debido al bombeo excesivo de agua y los retornos por riego. Handan are located in/near here (Fig. 1). Groundwater
resources are the key to agricultural development, and the
Keywords China . North China Plain . Tritium . demand for groundwater will increase in this area. With
Stable isotopes . Groundwater flow the development of the regional economy, the water use
environment has changed. The groundwater level has
lowered dramatically over the last half century owing to
Introduction the over-pumping of groundwater and to drought, accom-
panied by the expansion of saline-alkaline land area
The North China Plain (NCP), located at 112°30′E– (Nakayama et al. 2006).
119°30′E and 34°46′N–40°25′N, is a thick Cenozoic A great many studies about chemical and isotopic
sedimentary basin covering approximately 150,000 km2. characteristics of groundwater in the NCP have been

Fig. 1 Geomorphological map of the North China Plain (NCP)

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


reported. For instance, Chen et al. (2004) discussed the are: piedmont plain, alluvial fan plain, flood plain (alluvial
distribution characteristics of the isotopic composition and plain) and littoral plain (Wu et al. 1996b; Fig. 1). In this
average geochemical composition of groundwater in wells study, the focus is on the alluvial fan plain located in the
of different depths throughout the NCP. Hutuo River plain. Based on the results of field surveys
Geochemical characteristics change from recharge, and geochemical and isotopic analysis, the study empha-
intermediate, to discharge zone according to the regional sizes the following aspects: (1) confirmation/quantification
groundwater flow system (Stuyfzand 1999; Toth 1999; of the available groundwater resource using stable isotope
Chen et al. 2004). The use of the geochemical method to (18O and D) measurements; (2) flow velocity of ground-
estimate groundwater flow rates and mixing ratios is water recharged by modern precipitation using an expo-
effective for the NCP (e.g. Chen 1988; Chen et al. 2002; nential model of tritium concentration; and (3) spatial
Shimada et al. 2002). In the NCP, chemical patterns evolvement characteristics of stable isotopes and chemical
evolve from the recharge to the discharge zone in the composition. The work involved field survey, water
order: Ca–HCO3 > Mg–HCO3 > Na–Cl–SO4 (Chen et al. sampling and laboratory analysis, and provides a hydro-
2004). chemical background for protecting the water resource of
Natural stable isotopes and radiogenic isotopes ((H, O, the alluvial fan plain in the NCP.
3
H, 14C and 36Cl) of water have been widely used over the
past several decades to address problems related to
groundwater age, groundwater recharge, and delineation Study area and site description
of flow systems in the NCP. Groundwater age from wells
of 0–150 m depth in the NCP was estimated to be younger The North China Plain was formed over a long period of
than 25,000 years using 18O data (Chen et al. 2004) and time by flooding and course changes of several rivers
that from wells of 150–250 m and 341–456 m depth was which flow from the Taihang Mountains, or the Yanshan
found to be 25,000 years and 30,000 years respectively Mountains, through the plain and into the Bohai Sea (Wu
using 36Cl data (Zhou et al. 2001). The tritium concentra- et al. 1996a; Fig. 1). The rivers have interacted with the
tion in the NPC is high enough to be measured. In the flashy fluvial regime, and involve high sediment loads and
recharge area, the tritium contents are more than 6 tritium frequent channel changes (Xu et al. 1996a). Each river
units (TU), but they decrease to less than 1 TU along the played an important role in the formation of alluvial fans
flow path in the littoral plain. Modern groundwater is then at the front edge of the piedmont plain zone and in the
younger than about 45 years relative to the mid-1990s formation of the alluvial plains (Wu et al. 1996a). For
(Clark and Fritz 1997). Several studies have been carried example, there are large fluvial fans formed by the Yellow
out on groundwater age. For instance, Fritz et al. (1991) River, the Zhang River, the Hutuo River, the Yongding
carried out a study for groundwater in the waterloo River, the Chaobai River and the Luan River.
aquifer, Ontario, Canada. This study refined estimates for The study region is situated between a latitude 37°36′3″
groundwater mean residence time for water younger than to 38°39′28″ and a longitude 114°2′35″ to 115°29′24″
30 years to within a decade. (Fig. 2), and is one of the alluvial fan plain zones (Hutuo
There are four main geomorphological units in the River plain) mentioned above. The area has a continental,
North China Plain. From the piedmont to the coast, they semi-arid climate with a mean annual temperature of 12–

Fig. 2 Location of the wells, river water and spring sampling sites in the study area

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


13°C, and summer maximum and winter minimum of third dividing points in some channels, those of the late
45.8 and −28.2°C, respectively (Wu 1992) and with Holocene still form the alluvial fans (Wu et al. 1996b). On
annual precipitation of 400–800 mm (Yang et al. 2006). the alluvial fan plain, single channels are straight but the
The precipitation is dominated by the Asia summer pattern of the channels is radial, which means that there is
monsoon during July and August, which accounts for an apex at the top of a fan from which a number of
about 70% of annual precipitation (Zhang et al. 2000). palaeochannels run in different directions (Wu et al.
There is usually only 40–60 mm of rainfall, or even no 1996b). These palaeochannels are formed by the combi-
rainfall, for more than 100 days in spring. The variation of nation of sand bodies of a number of meandering channels
seasonal precipitation is so large that it is the common and are beaded in shape. The particle size is smaller; and
case to have dry spring and flooding summer. Mean the sand layer is thinner (3–5 m) than those of the other
potential evaporation ranges from 1,100 to 1,800 mm (Liu stage palaeochannels. Most of these palaeochannels lie
and Wang 1992). between sandy elevated palaeochannel zones (Wu et al.
Vertical distribution of the aquifer has been described 1996b). The alluvial fan plain surfaces and the uppermost
in detail. A thick sedimentary sequence has been 10 m of sediments were formed by river deposits during
deposited in the NCP, with a depth of 500–600 m in the late Holocene and are recorded in historical docu-
depressions, 350–450 m in uplift areas, and 150–300 m ments. The lower sediments consist of micro cross-bedded
around the alluvial fan (Zhou et al. 2001). These sedi- and trough cross-bedded medium and fine sand with grain
ments of the Quaternary layer are composed of four sizes of 1–4 Ø, small gravels and pieces of brick. The
layers: an unconfined layer of fine sand and silt to 40– upper sediments consist of horizontally bedded silt and
60 m depth; a confined layer of sand and gravel to 100– sandy soil (Fig. 4) with grain sizes of 3–6 Ø. The
150 m depth; a confined layer of course sand and gravel to radiocarbon age for these sediments is less than
250–350 m depth; and a confined layer of fine sand and 2,500 years BP (Wu et al. 1996a).
gravel to bedrock at 400–600 m depth (Zhang et al. 2000;
Chen et al. 2005; see Fig. 3). The alluvial fan plain slopes
generally eastward from an altitude of about 100 m above Materials and methods
sea level (m.a.s.l.) in the west to about 1–2 m in the east.
During the late Pleistocene, the diversion points of the Water sampling and chemical analysis
Hutuo River were located around Huangbizhuang, form- Groundwater of the alluvial fan plain zone in NPC was
ing the old mountain front fan (Xu et al. 1996b). By the sampled during 1999–2000. Seven stretches of the Beisha
late Holocene, the diversion points had moved down- River (a tributary of Hutuo River; samples collected at the
stream to Gaocheng, forming a new alluvial fan. These base of Taihang Mountain and Beisha River were
points around Gaocheng are along the NNE Anguo- considered as recharge to groundwater), six springs and
Gaocheng fault (Shao et al. 1984). Alluvial fans were 31 wells with depths ranging from 0 m (river waters) to
formed from which the palaeochannels are radially 150 m were surveyed (Fig. 2). The Cl−, SO2 4 and
NO 3
distributed again. Although there are second, and even contents were analyzed by ion chromatography; K , Na+,
+

Fig. 3 Hydrogeologic cross section along transect O–O’ in Fig. 1 (modified from Chen et al. 2005)

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


Fig. 4 Simplified hydrostratigraphic map of the alluvial fan

Ca2+, Mg2+ were measured by inductively coupled plasma 12.43 years (Unterweger et al. 1980). Atmospheric testing
(ICP) with analytical precision of ±0.01 mg/l; and HCO
3 of nuclear devices between 1952 and 1962 generated a
was measured by titration with analytical precision of tremendous quantity of atmospheric tritium. The final year
±0.02 mg/l. of megaton tests generated a huge peak, which appeared
in precipitation in the spring of 1963. So the curve from
the input function for tritium will have a peak corre-
Stable isotope analysis sponding to that time. Using this peak, one can get the
18
O and deuterium (D) abundances are expressed as ratios mean residence time and infiltration rate of water. In
in delta notation (δ) as per mil differences relative to the Denmark, Andersen and Sevel (1974) have shown that the
standard known as the Vienna Standard Mean Ocean measured tritium profile in groundwater is the reverse of
Water (VSMOW). They are defined as follows: the classic curve for tritium in precipitation.
  In general terms, consider that there is a parcel of
Rsp groundwater in a regional aquifer. The composite of
d 18 Oðd DÞ ¼  1  1000 ð1Þ several years’ precipitation have contributed to ground-
Rst
water through mixing in the unsaturated zone. In this
Where Rsp and Rst are the ratios for D/1H or 18O/16O in the process, tritium content in groundwater will decrease by
sample or standard respectively. δ18O and δD were decay. The tritium concentration in this groundwater
analyzed by a Delta S mass spectrometer with analytical parcel will be a function of its residence time in the
precision of ±0.15 and ±1‰, respectively. recharge environment. The exponential model of tritium
concentration is predicted by

A tritium profile peak and input function for tritium Z1    


1
in groundwater and tritium analysis C ðt Þ ¼ CR ðt   Þ  expð Þ   exp   d ð2Þ
T T
Tritium (3H or T) is probably the most commonly 0
employed radioisotope used to identify modern recharge.
It is a short-lived isotope of hydrogen with a half-life of l ¼ 1=Tl ¼ In2=sTh

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


where Th is the half-life of tritium, T is the mean residence 2004), the groundwater was separated into a vertical two-
time, CR(t) is tritium concentration in precipitation, and C layer structure (the upper layer and the lower layer) with a
(t) is the recharged tritium concentration. If CR(t) can be boundary at 80–100 m depth.
acquired, the mean residence time T will be calculated by C
(t). The tritium content of water samples was analyzed by
the Institute of Hydrogeology and Engineering Geology, Geochemical characteristics of groundwater
Chinese Academy of Geological Sciences, Zhengding. and surface water
Ion concentrations in the two layers were different
(Table 2). Cl−, Ca2+ and NO 3 ion concentrations were
Results higher in the upper layer, and HCO 2 +
3 , SO4 and Na ion
concentrations were higher in the lower layer. Figure 5
Chemical and isotopic data of samples are shown in shows the relation between the major ion concentrations
Table 1. The depths of the wells sampled are from 8.5 to (Cl−, HCO 2  + 2+ + 2+
3 , SO4 , NO3 , Na , Ca , K , Mg ) and the
150 m (Table 1). Based on vertical distribution of the depths of the wells in the alluvial fan. The major ions
aquifer mentioned above (Yang et al. 2001; Chen et al. might be divided into three types: one type is Cl−, SO2
4 ,

Table 1 Chemical and isotopic data of samples


Sample/ Sample Well Ca2+ Mg2+ Na+ K+ HCO 3 Cl− SO2
4 NO3 δ18O δD Tritium
site no. type depth (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (‰) (‰) (TU)
(m)
R1 River ― 31.94 12.1 4.94 2.37 65.47 3.57 81.32 10.44 −9.52 −66.18 22.23
R2 River ― 87.82 17.43 13.43 2.52 189.53 17.83 102.37 53.33 −8.75 −77.01 18.5
R3 River ― 95.81 20.58 19.54 2.64 195.27 32.1 105.24 72.73 −9.27 −78.57 21.59
R4 River ― 87.82 21.79 18.98 2.97 141.28 28.53 138.73 73.94 −7.51 −64.46 22.02
R5 River ― 67.86 18.64 9.17 1.72 189.53 15.69 66.97 40.16 −8.64 −72.26 21.87
R6 River ― 73.85 19.37 21.34 3.2 172.3 19.26 103.33 43.86 −8.54 −60.49 19.74
R7 River ― 72.65 20.58 6.52 1.37 183.78 7.85 74.63 40.97 −8.7 −73.38 21.05
G1 GW 8.5 127.74 27.84 21.06 3.01 189.53 39.23 162.65 150.56 −8.66 −74.32 23.85
G2 GW 24 95.81 35.10 22.35 1.27 344.59 44.94 66.97 35.16 −8.21 −68.09 38.84
G3 GW 25 183.12 36.29 52.98 5.32 384.40 72.20 147.44 60.97 −8.4 −59 26.8
G4 GW 25 127.74 34.38 31.58 2.55 402.02 46.37 116.72 17.82 −7.05 −72.74 23.51
G5 GW 27 71.86 21.79 18.52 1.53 195.27 17.83 100.46 32.32 −8.61 −68.3 26.59
G6 GW 28.5 85.83 13.31 13.80 0.73 229.73 28.53 62.19 25.32 −8.47 −72.89 30.83
G7 GW 30 87.82 24.21 26.89 1.17 246.96 39.23 114.81 64.33 −8.7 −64 15.6
G8 GW 30 211.36 47.58 88.19 4.69 367.30 284.20 85.52 11.20 −7.18 −62.06 21.22
G9 GW 30 57.03 23.59 35.74 7.77 185.50 60.63 57.97 0.00 −7.67 −59.06 15.65
G10 GW 31 73.85 21.30 14.07 0.91 206.76 28.53 79.41 26.30 −8.66 −76.83 31.29
G11 GW 34 65.87 9.68 9.92 0.88 212.50 21.40 23.92 12.67 −8.82 −78.99 19.07
G12 GW 35 101.80 67.78 41.39 1.11 476.69 92.73 81.32 28.99 −7.89 −60.48 21.36
G13 GW 40 93.81 19.58 15.56 1.55 298.65 32.10 49.75 ― −8.4 −64.3 28.1
G14 GW 40 41.00 45.00 29.10 1.11 313.00 34.00 11.00 ― −8.6 −65.2 23.5
G15 GW 40 191.54 41.35 25.47 6.15 294.85 53.94 140.79 ― −8.3 −65.2 25.2
G16 GW 40 94.00 67.00 41.50 1.89 407.00 62.00 165.00 27.78 −8.84 −72.71 24.15
G17 GW 40 35.00 42.00 12.40 1.95 315.00 36.00 15.00 0.00 −8.52 −66.25 14.75
G18 GW 45 95.01 33.89 21.97 1.77 292.90 21.40 108.11 47.81 −8.13 −75.36 22.93
G19 GW 50 24.27 18.89 60.69 1.52 284.60 1.66 20.16 ― −9.24 −68.82 16.29
G20 GW 60 66.46 36.83 22.27 2.72 304.61 57.95 2.69 ― −7.5 −59.7 12.2
G21 GW 70 51.10 19.37 16.73 1.32 235.47 32.10 7.65 5.61 −8.75 −80.72 11.15
G22 GW 80 22.00 39.00 15.90 0.86 263.00 25.00 5.00 ― −8.4 −66.4 9.4
G23 GW 80 56.19 13.45 12.80 2.54 216.25 16.47 30.67 ― −9.3 −68.62 11.89
G24 GW 80 26.38 16.35 63.05 2.66 294.85 12.44 28.66 ― −9.75 −72.69 7.53
G25 GW 100 70.30 28.98 14.75 2.47 296.80 31.43 68.61 ― −10.56 −81.83 10.96
G26 GW 110 64.13 29.92 47.77 2.75 269.70 56.20 27.79 ― −8.8 −64 1.9
G27 GW 120 34.63 17.81 70.55 3.93 213.60 92.30 76.66 ― −9.8 −70 0.4
G28 GW 135 34.65 23.16 250.55 1.87 693.19 30.51 266.26 0.10 −9.7 −72 0.4
G29 GW 120 62.00 67.00 94.30 1.80 335.00 60.00 180.00 ― –7.8 –64.3 6.4
G30 GW 130 55.47 18.05 24.63 5.97 183.10 6.80 25.24 7.77 –9.6 –63 5.3
G31 GW 150 84.08 46.84 148.03 5.83 265.07 101.02 336.90 ― −10.21 −76.97 3.91
S1 Spring ― 83.83 46.00 27.77 1.42 252.70 44.94 189.44 21.46 −8.95 −62.38 17.64
S2 Spring ― 89.02 29.05 17.13 2.05 246.96 28.53 120.55 20.80 −8.86 −58.95 18.43
S3 Spring ― 59.88 19.37 8.60 1.79 149.32 10.70 95.68 39.21 −8.81 −64.39 21.54
S4 Spring ― 49.90 19.37 9.20 1.42 229.73 3.57 28.70 45.18 −8.91 −61.26 22.54
S5 Spring ― 71.86 19.37 11.49 4.57 172.30 14.27 74.63 22.25 −8.8 −65.37 20.18
S6 Spring ― 87.82 21.79 4.79 1.35 212.50 10.70 79.41 6.09 −9.09 −81.42 19.42
GW groundwater from wells

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


Table 2 Statistics for the two layers of groundwater in the alluvial fan area (unit of ion concentration: mg/l)
Layer Depth (m) Cl− HCO
3 SO2
4 NO
3 Na+ Ca2+ K+ Mg2+
Upper layer 0–80 Min 1.66 185.5 2.69 0 9.92 22 0.73 9.68
Max 284.2 476.7 165 150.56 88.2 211.36 7.77 67.78
Lower layer 100–150 Min 6.8 183.1 25.24 0 14.75 34.63 1.80 17.81
Max 101.02 693.2 336.9 7.77 250.55 84.08 5.97 67

Na+ and K+, the second type is and Ca2+, and the third the upper layer, ion concentration decreased as the well
type is NO3. depth increased. However, nitrate was undetectable in the
The upper layer (0–80 m) is an unconfined layer of fine lower layer. The difference in NO 3 ion distribution
sand and silt, and all ion concentrations varied widely. The between the two layers reflects a change in the influence
concentrations of Cl−, SO2 + +
4 , Na and K decreased as of human activities.

the well depth increased. Likewise, HCO3 and Ca2+ (the In the springs, Cl−, SO2 
4 , HCO3 and NO3 ion


second water type) decreased with the well depth in this concentrations were 3.57–44.94 mg/l, 28.7–189.44 mg/l,
layer. The lower layer (100–150 m) is a confined layer of 149.32–252.7 mg/l and 6.09–45.18 mg/l respectively.
sand and gravel; depth 80–100 m is the boundary of the Na+, Ca2+, K+ and Mg2+ ion concentrations were 4.79–
upper and the lower layer. Cl−, SO2 4 , Na+ and K+ ion 27.77 mg/l, 49.9–89.02 mg/l, 1.35–4.57 mg/l and 19.37–
concentrations increased with the well depth, and there 46 mg/l respectively (Table 1). The range of ion
was no significant increase in and Ca2+ ion concentration concentrations was close to the groundwater in the upper
with increasing depth. Groundwater in this lower layer is layer, and springs were recharged by groundwater of the
used because of the decline in the water table. upper layer.
Nitrate is the most common water contaminant index In the river water, Cl−, SO2  
4 , HCO3 and NO3 ion
for anthropogenic sources (Freeze and Cherry 1979). In concentrations were 3.57–32.1 mg/l, 66.97–138.73 mg/l,

Fig. 5 The distribution of ion concentrations (Cl−, HCO 2  + 2+ + 2+


3 , SO4 , NO3 , Na , Ca , K , Mg ) versus the depths of the wells. Dashed lines
indicate the variation area of major ion concentrations

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


Fig. 6 The distribution of ion concentration in river water versus east longitude

65.47–195.27 mg/l and 10.44–73.94 mg/l respectively, −80.72 to −59‰ respectively. The δ18O values decreased
and showed the highest NO3 concentration compared with with the well depth, but the change of δD values was not
that in the groundwater. Na+, Ca2+, K+and Mg2+ ion obvious. In the lower layer, the δ18O and δD values
concentrations were 4.94–21.34, 31.94–95.81, 1.37–3.2 ranged from −10.56 to −7.8‰ and from −81.83 to −63‰,
and 12.1–21.79 mg/l respectively (Table 1). Beisha River respectively. The δ18O and δD values decreased with the
flows from west to east in the study area. Na+, Ca2+ and well depth in this layer. Groundwater in the upper layer
all anion concentrations increased along river flow had greater δ18O than that in the lower layer.
direction (Fig. 6). The δ18O and δD values in the river water ranged from
−9.52 to −7.51‰ and −78.57 to −60.49‰ respectively
and showed the lower isotopic values. On the other hand,
Isotopic characteristics of groundwater the δ18O and δD values in the spring ranged from −9.09 to
and surface water −8.8‰ and −81.42 to −58.95‰, respectively (Table 1).
Stable isotopes of water are excellent tracers for recharge
of surface water to groundwater (Craig et al. 2002). 18O
and D are naturally occurring stable isotopes of oxygen Tritium characteristics of groundwater
and hydrogen, respectively (John et al. 2002). Stable and surface water
isotopes show different changes between the upper and Generally, the tritium contents of groundwater from wells
lower groundwater layers (Fig. 7). In the upper layer, the are higher in the upper layer (7.53–38.84 TU) than in the
δ18O and δD values ranged from −9.75 to −7.05‰ and lower layer (less than 11 TU; Table 1). River and spring

Fig. 7 The distribution of δ O and δ D versus the depths of the wells. Dashed lines indicate the variation area
18

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


Fig. 8 Relationship between δ 18O and δ D in the water samples. MWL (meteoric water line) is the relationship between δ18O and δD in
meteoric water (δD=8δ18O+d; here d=0, −10). GMWL is MWL with d=10‰

water shows the higher tritium contents (greater than been subjected to significant evaporation during infiltra-
17 TU). tion into the aquifer. The intercept is often referred to as
the deuterium-excess (d-excess), defined as d ¼ d D 
8d 18 O (Dansgaard 1964). The d-excess is a useful proxy
Discussion for identifying secondary processes influencing the atmo-
spheric vapor content in the evaporation-condensation
The source of groundwater and surface water cycle in nature (Craig 1961; Merlivat and Jouzel 1979).
Because most of the world’s precipitation is derived from The d-excess values of groundwater samples ranged from
evaporation of seawater, the δ18O and δD composition of −10 to 10‰ in the upper layer and from 0 to 10‰ in the
precipitation throughout the world is linearly correlated. lower layer (Fig. 8). It can be considered that the
This relation is known as the global meteoric water line groundwater originates from rainfall with different d-
(GMWL) and expressed as follows (Craig 1961): excess values. On the other hand, based on hydrology and
d D ¼ 8d 18 O þ 10. human activities, the upper flow system has been affected
The δ18O and δD composition of all water samples in by many phenomena such as (1) location of Hutuo River
the study region were plotted to the right of the global in the center of the alluvial fan plain, (2) excess irrigation
meteoric water line (GMWL; Fig. 8). From the relation- water return flow to the aquifer.
ship shown in Fig. 8, all of the points in the upper According to the study of Zhang et al. (2000), a δ18O
groundwater layer were under the GMWL and the linear value of less than −9‰ signifies groundwater older than
relationship is approximately parallel to the GMWL, 10,000 years in the NCP because the climate became
showing that groundwater of study area has been warm 10,000 years ago. Whereas, if the groundwater is
recharged by precipitation and these samples have not younger than 10,000 years, the δ18O value would be

Fig. 9 Relationship between δ 18


O and tritium in the water samples

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


20 TU, implying that these samples were a mixture of new
water and old water.

Groundwater flow system and flow velocity based


on tritium
Based on δ18O and δD values mentioned above, the range
of ages in the two groundwater layers can be determined.
Based on tritium values, modern groundwater age and
flow velocity can be determined. As the era of bomb
testing recedes further into the past, the tritium peak has
either moved through actively circulating aquifers or has
been attenuated by dispersion and mixing. Nonetheless, it
may be preserved in some less active hydrogeological
settings. The distribution of tritium suggests that ground-
water in the alluvial fan plain above a depth of 150 m
contains modern recharge water. However, modern re-
charge only influences the shallow groundwater in the
middle and the littoral plain and not the deep confined
aquifers (Chen et al. 2003). The tritium concentrations in
river water and groundwater had a strong exponential
Fig. 10 The distribution of tritium versus the depths of the wells. dependence relation to well depth in the upper layer
Dashed lines indicate the variation area (Fig. 10). The tritium value reached a peak at 20 m depth,
in which it is 40 TU. Then, tritium values decreased as the
well depth increased. The lowest value was 7.53 TU in the
upper layer; in the lower layer the lowest value was less
greater than −9‰. In the upper layer, δ18O values of than 15 TU.
samples were higher than −9‰ except G19, G23 and On the basis of data from the International Atomic
G24; in the lower layer, δ18O value of G29 and G26 was Energy Agency (IAEA), the distribution graph of tritium
higher than −9‰, and the others were lower than −9‰ concentration in global meteoric water can be described.
(Fig. 9). It can be considered that groundwater in the Based on tritium values of river water in Fig. 10, tritium
upper layer and groundwater of G29 and G26 in the lower concentration of rainfall in the NCP was 18–22 TU. In
layer was younger than 10,000 years (modern water) in addition, modern water (groundwater in the upper layer;
the alluvial fans. In the NCP, the tritium value of rainfall Fig. 9) was supplied by modern rainfall. In this study, it is
that is older than 10,000 years is considered to be close to considered that groundwater is recharged from rainfall and
0 TU, so the groundwater in the lower layer is a mixture the peak value of tritium contents is due to the
of new water and old water. Almost all river water and atmospheric testing of thermonuclear bombs between
spring water is younger than 10,000 years, except R1, R3 1952 and 1962. Using the model described in Eq. (2) the
and S6. Tritium values of R1, R3 and S6 were higher than tritium input can be determined on the basis of measured

Fig. 11 Tritium distribution in groundwater of a the upper layer and b the lower layer versus east longitude. Dashed lines indicate the
variation area

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


Fig. 12 The vertical distribution of δ 18
O (‰) in groundwater along transect O–O’. Arrows shows the flow direction

tritium data. From the model, it can be considered that the tritium concentration. By the exponential model, it can be
vertical velocity of groundwater in the upper layer is less calculated that horizontal flow velocity is faster than
than 1 m/year. vertical velocity. Tritium contents decreased as latitude
In the upper groundwater layer, tritium contents of increase in the lower layer (Fig. 11b). It is considered that
horizontal distribution (along O–O` in Fig. 2) reached a the flow direction of groundwater in the lower layer is
peak at about 114.5° E (Fig. 11a). As mentioned above, an from west to east, so tritium contents decrease with the
exponential model can be educed from the distribution of groundwater flow.

Fig. 13 Piper diagram for the major ions in groundwater (from wells), river water and spring water in the study area

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


Fig. 14 The vertical distribution of the hydrochemical composition of groundwater along transect O–O’

Spatial evolvement characteristics of stable isotopes type is probably related to ion exchange between
and chemical composition groundwater and groundwater that is mainly excess
Because the groundwater level is higher in the mountain- irrigation return. Every time the return water re-percolates
ous areas, groundwater constantly flows into the plain, and through the soil profile, it dissolves more salts, resulting in
the mountainous area plays an important role as a recharge the mixed chemistry as shown in Fig. 14.
region (Nakayama et al. 2006; Fig. 12). In the NCP,
almost all of irrigation water is pumped up from
underground. The excess irrigation water returns to the Protection of the groundwater resource
aquifer by infiltration. Because it infiltrates into the aquifer The NCP is one of the most important agricultural areas in
directly, evaporation and oxygen isotope shift have less China. Groundwater storage and quality are affected by
influence on it. The δ18O values of the groundwater in agricultural irrigation and industrial development. Because
some places (e.g. G19, G23 and G24) were low compared the agricultural irrigation water and some industrial and
with most places in the upper layer (Fig. 12). This implied domestic use water come from aquifers, the groundwater
that the irrigation has an influence on the aquifer. There level has a downward trend and water quality is getting
are a lot of irrigation wells in the alluvial fan plain leading worse. NO 3 concentrations from about 18% of water
to excessive groundwater use as well as irrigation return samples were higher than the water quality standard for
(water returned to the aquifer after use). drinking water sources (NO 3 : 44 mg/l; Ministry of Health
The Piper diagram (Piper 1944) is the most widely of the People’s Republic of China 2006; Table 1). The
used graphical form to express geochemistry results and it authors herein suggest that management of the groundwa-
is quite similar to the diagram proposed by Hill (1940). ter resource includes three points. Firstly, irrigation
The diagram displays the relative concentrations of the management should be carried out under scientific
major cations and anions on two separate trilinear plots direction; good planning of irrigation in dry years is
(Güler et al. 2002). The points of the central diamond are especially important for saving water (Yang et al. 2006).
from the two trilinear plots (Güler et al. 2002). The central Secondly, the management system of industrial and city
diamond-shaped field is used to show overall chemical water use should be optimized; and thirdly, the monitoring
character of the water (Hill 1940; Piper 1944). Figure 13 of wastewater discharge and disposal should be intensified.
is a Piper diagram showing the results of the river, spring
and well samples in the alluvial fan plain. The river and
spring waters were distinctive in their low concentrations Conclusions
of Na+ and Cl− and the type was HCO3–NO3–Ca. Because
of the effect of carbonate rock and metamorphic rock in In this study, water quality, stable isotopes and tritium
the mountains region (Fig. 4), groundwater in the upper were used to determine the groundwater flow path. The
layer was characterized by Ca–HCO3. On the other hand, main findings can be summarized as follows:
groundwater points in the lower layer were broadly
distributed rather than forming distinct clusters. Ground- 1. The δ18O and δD values ranged from −10.56 to
water in the lower layer was classified into two dominant −7.05‰ and −81.83 to −59‰ respectively. The
water types: HCO3–Ca–Mg and HCO3–Na–K. groundwater in the upper layer originates from rainfall
In the discharge area, groundwater was characterized with different d-excess values, and has not been
by Na–HCO3 type (Fig. 14). Formation of this chemical subjected to significant evaporation during infiltration

Hydrogeology Journal DOI 10.1007/s10040-008-0292-3


into the aquifers. Groundwater in the upper layer is Hill RA (1940) Geochemical patterns in Coachella Valley. Trans
younger than 10,000 years. Am Geophys Union 21:46–49
John AI, John R, Robert LM (2002) Movement of water through the
2. Groundwater flow velocity can be determined using a thick unsaturated zone underlying Oro Grande and Sheep Creek
tritium model, but a tritium exponential model cannot washes in the western Mojave Desert, USA. Hydrogeol J
be used to identify age of old water. In the alluvial fan 10:409–427
plain, the groundwater flow velocity is in the order: Liu C, Wang P (1992) The environment significance of isotope
composition in groundwater of Hebei Plain. In: Proceedings of
horizontal flow velocity > vertical velocity. Vertical International Workshop on Groundwater and Environment.
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3. Irrigation has an influence on the aquifer. The Merlivat LJ, Jouzel (1979) Global climatic interpretation of
distribution of δ18O along a cross section from west deuterium-oxygen relationship for precipitation. J Geophys
to east (O–O’) could imply that water was withdrawn Res 84:5029–5033
Ministry of Health of the People’s Republic of China (2006) Water
from the aquifer for irrigation, and then returned to the quality standard for drinking water sources in China, Ministry
aquifer after use. of Health, Beijing
4. Because of the effect of carbonate rock and metamor- Nakayama T, Yang Y, Watanabe M, Zhang X (2006) Simulation of
phic rock in the mountains region groundwater in the groundwater dynamics in the North China Plain by coupled
hydrology and agricultural models. Hydrol Process 20:3441–
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probably related to ion exchange between groundwater interpretation of water analyses. Trans Am Geophys Union
and recycled groundwater that is mainly excess 25:914–923
Shao S, Zhonggyuan A, Han S (1984) Analysis on the main
irrigation water return. characteristics of the neotectonic movement in the Hebei Plain.
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Hydrogeology Journal DOI 10.1007/s10040-008-0292-3

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