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Spatial characteristics of water quality, stable isotopes and tritium associated with groundwater ow 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 ow system and the ow velocity in the alluvial fan plain of the Hutuo River, China, have been studied, with an emphasis on relating geochemical characteristics and isotopes factors. Seven stretches of one river, six springs and 31 wells, with depths ranging from 0 m (river waters) to 150 m, were surveyed. The groundwater has a vertical two-layer structure with a boundary at about 80100 m depth, yielding an upper and a lower groundwater layer. The

δ

O and δ D values range from 10.56 to 7.05and 81.83 to 59 , respectively. The groundwater has been recharged by precipitation, and has not been subjected to signicant evaporation during inltration into the aquifer in the upper layer. Using a tritium model, the groundwater ow in the alluvial fan plain showed horizontal ow velocity to be greater than vertical velocity. Groundwater in the upper layer is characterized by Ca HCO 3 type. From the spatial distribution characteristics of the stable isotope and chemical composition of the groundwater, agricultural irrigation was considered to have an inuence

18

Received: 15 May 2006 /Accepted: 17 February 2008

© Springer-Verlag 2008

Y. Lu ( ) ) : F. Li

Graduate School of Science and Technology,

Chiba University Chiba 2638522, Japan e-mail: yintaolu2003@yahoo.co.jp

C. Tang

Faculty of Horticulture, Chiba University

Chiba 2718510, Japan

J. Chen

Zhongshan University Guangzhou 510275, China

X. Song

Institute of Geographic Sciences

and Natural Resources Research Beijing 100101, China

Y. Sakura

Faculty of Science, Chiba University

Chiba 2638522, Japan

on the aquifer by causing excessive groundwater abstrac- tion and irrigation return.

Résumé Le système découlement de leau souterraine et la vitesse découlement dans le plaine du cône alluvial de la Rivière Hutuo, Chine, ont été étudiés en mettant laccent sur les caractéristiques géochimiques et les facteurs isotopiques correspondants. Sept tronçons dune rivière, six sources et 31 puits, ayant des profondeurs allant de 0 m (eau de la rivière) à 150 m, ont été examinés. Leau souterraine a une structure verticale à deux couches avec une limite à environ 80100 m de profondeur, formant une couche supérieur

deau souterraine et une inférieure. Les valeurs de

de D vont de 10.56 à 7.05et de 81.83 à 59, respectivement. Leau souterraine a été réalimentée par les précipitations, et na pas été sujette à une évaporation signicative au cours de linltration dans laquifère de la couche supérieure. En utilisant modèle tritium, lécoulement de leau souterraine dans la plaine du cône alluvial a montré une vitesse découlement horizontal supérieure à la vitesse verticale. Leau souterraine de la couche supérieure est caractérisée par un type CaHCO 3 . Du fait des caractéris- tiques de la distribution spatiale en isotope stable et de la composition chimique de leau souterraine, lirrigation agricole a été jugée avoir une inuence sur laquifère en occasionnant des prélèvements deau souterraine et une restitution provenant de lagriculture excessifs.

O et

18

Resumen Se ha estudiado el sistema de ujo subterráneo y la velocidad de ujo en el cono aluvial del Río Hutuo, China, enfatizando las características geoquímicas y su relación con el contenido isotópico. Se relevaron siete tramos del río, seis manantiales y 31 pozos, con profundidades que varían desde 0 m (agua del río) hasta 150 m. El complejo subterráneo comprende dos capas con un límite a una profundidad aproximada de 80100 m, constituyendo una capa subterrá- neas superior y una inferior. Los valores de δ 18 O yδD varían entre 10.56 a 7.05y 81.83 a 59, respectivamente. El agua subterránea se recargó por lluvias, y no ha estado sujeta a evaporación durante su inltración en la capa superior del acuífero. El modelo de ujo subterráneo, utilizando datos de tritio, mostró que la velocidad del ujo horizontal es mayor que la vertical. El agua subterránea de la capa superior es del tipo CaHCO 3 . Teniendo en cuenta la

distribución espacial de los isótopos estables y la compo- sición química del agua subterránea, se considera que el riego para agricultura ha tenido inuencia en el acuífero debido al bombeo excesivo de agua y los retornos por riego.

Keywords China . North China Plain . Tritium . Stable isotopes . Groundwater ow

Introduction

The North China Plain (NCP), located at 112°30 E 119°30 E and 34°46 N 40°25 N, is a thick Cenozoic sedimentary basin covering approximately 150,000 km 2 .

This is one of the most im portant areas for both groundwater storage and human activity in China. Big cities with huge population, e.g. Beijing, Shijiazhuang and Handan are located in/near here (Fig. 1). Groundwater resources are the key to agricultural development, and the demand for groundwater will increase in this area. With 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 the over-pumping of groundwater and to drought, accom- panied by the expansion of saline-alkaline land area (Nakayama et al. 2006). A great many studies about chemical and isotopic characteristics of groundwater in the NCP have been

isotopic characteristics of groundwater in the NCP have been Fig. 1 Geomorphological map of the North

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

reported. For instance, Chen et al. (2004) discussed the distribution characteristics of the isotopic composition and average geochemical composition of groundwater in wells of different depths throughout the NCP. Geochemical characteristics change from recharge, intermediate, to discharge zone according to the regional groundwater ow system (Stuyfzand 1999; Toth 1999; Chen et al. 2004). The use of the geochemical method to estimate groundwater ow rates and mixing ratios is effective for the NCP (e.g. Chen 1988; Chen et al. 2002; Shimada et al. 2002). In the NCP, chemical patterns evolve from the recharge to the discharge zone in the order: Ca HCO 3 > MgHCO 3 > NaClSO 4 (Chen et al.

2004).

Natural stable isotopes and radiogenic isotopes ((H, O, 3 H, 14 C and 36 Cl) of water have been widely used over the past several decades to address problems related to groundwater age, groundwater recharge, and delineation of ow systems in the NCP. Groundwater age from wells of 0150 m depth in the NCP was estimated to be younger than 25,000 years using 18 O data (Chen et al. 2004) and that from wells of 150250 m and 341 456 m depth was found to be 25,000 years and 30,000 years respectively using 36 Cl data (Zhou et al. 2001). The tritium concentra- tion in the NPC is high enough to be measured. In the recharge area, the tritium contents are more than 6 tritium units (TU), but they decrease to less than 1 TU along the ow path in the littoral plain. Modern groundwater is then younger than about 45 years relative to the mid-1990s (Clark and Fritz 1997). Several studies have been carried out on groundwater age. For instance, Fritz et al. ( 1991) carried out a study for groundwater in the waterloo aquifer, Ontario, Canada. This study rened estimates for groundwater mean residence time for water younger than 30 years to within a decade. There are four main geomorphological units in the North China Plain. From the piedmont to the coast, they

are: piedmont plain, alluvial fan plain, ood plain (alluvial plain) and littoral plain (Wu et al. 1996b; Fig. 1). In this study, the focus is on the alluvial fan plain located in the Hutuo River plain. Based on the results of eld surveys and geochemical and isotopic analysis, the study empha- sizes the following aspects: (1) conrmation/quantication of the available groundwater resource using stable isotope ( 18 O and D) measurements; (2) ow velocity of ground- water recharged by modern precipitation using an expo- nential model of tritium concentration; and (3) spatial evolvement characteristics of stable isotopes and chemical composition. The work involved eld survey, water sampling and laboratory analysis, and provides a hydro- chemical background for protecting the water resource of the alluvial fan plain in the NCP.

Study area and site description

The North China Plain was formed over a long period of time by ooding and course changes of several rivers which ow from the Taihang Mountains, or the Yanshan Mountains, through the plain and into the Bohai Sea (Wu et al. 1996a; Fig. 1). The rivers have interacted with the ashy uvial regime, and involve high sediment loads and frequent channel changes (Xu et al. 1996a). Each river played an important role in the formation of alluvial fans at the front edge of the piedmont plain zone and in the formation of the alluvial plains (Wu et al. 1996a). For example, there are large uvial fans formed by the Yellow River, the Zhang River, the Hutuo River, the Yongding River, the Chaobai River and the Luan River. The study region is situated between a latitude 37°363to 38°39 28and a longitude 114°2 35 to 115°2924 (Fig. 2 ), and is one of the alluvial fan plain zones (Hutuo River plain) mentioned above. The area has a continental, semi-arid climate with a mean annual temperature of 12

semi-arid climate with a mean annual temperature of 12 – Fig. 2 Location of the wells,

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

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 annual precipitation of 400 800 mm (Yang et al. 2006). The precipitation is dominated by the Asia summer monsoon during July and August, which accounts for about 70% of annual precipitation (Zhang et al. 2000). There is usually only 40 60 mm of rainfall, or even no

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 case to have dry spring and ooding summer. Mean potential evaporation ranges from 1,100 to 1,800 mm (Liu and Wang 1992 ). Vertical distribution of the aquifer has been described in detail. A thick sedimentary sequence has been deposited in the NCP, with a depth of 500 600 m in depressions, 350450 m in uplift areas, and 150300 m around the alluvial fan (Zhou et al. 2001). These sedi- ments of the Quaternary layer are composed of four layers: an unconned layer of ne sand and silt to 40 60 m depth; a conned layer of sand and gravel to 100 150 m depth; a conned layer of course sand and gravel to 250350 m depth; and a conned layer of ne sand and 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 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 Hutuo River were located around Huangbizhuang, form- ing the old mountain front fan (Xu et al. 1996b). By the late Holocene, the diversion points had moved down- stream to Gaocheng, forming a new alluvial fan. These points around Gaocheng are along the NNE Anguo- Gaocheng fault (Shao et al. 1984). Alluvial fans were formed from which the palaeochannels are radially distributed again. Although there are second, and even

contents were analyzed by ion chromatography; K + , Na + ,

Holocene still form the alluvial fans (Wu et al. 1996b). On the alluvial fan plain, single channels are straight but the pattern of the channels is radial, which means that there is an apex at the top of a fan from which a number of palaeochannels run in different directions (Wu et al. 1996b). These palaeochannels are formed by the combi-

and are beaded in shape. The particle size is smaller; and the sand layer is thinner (35 m) than those of the other stage palaeochannels. Most of these palaeochannels lie between sandy elevated palaeochannel zones (Wu et al. 1996b). The alluvial fan plain surfaces and the uppermost 10 m of sediments were formed by river deposits during the late Holocene and are recorded in historical docu- ments. The lower sediments consist of micro cross-bedded and trough cross-bedded medium and ne sand with grain sizes of 14 Ø, small gravels and pieces of brick. The upper sediments consist of horizontally bedded silt and sandy soil (Fig. 4) with grain sizes of 36 Ø. The radiocarbon age for these sediments is less than 2,500 years BP (Wu et al. 1996a ).

Materials and methods

Water sampling and chemical analysis

Groundwater of the alluvial fan plain zone in NPC was sampled during 19992000. Seven stretches of the Beisha River (a tributary of Hutuo River; samples collected at the base of Taihang Mountain and Beisha River were considered as recharge to groundwater), six springs and 31 wells with depths ranging from 0 m (river waters) to

150 m were surveyed (Fig. 2). The Cl , SO

2

4

and NO

3

surveyed (Fig. 2 ). The Cl − , S O 2 4 and NO 3 Fig.

Fig. 3

Hydrogeologic cross section along transect O O in Fig. 1 (modi ed from Chen et al. 2005)

Fig. 4 Simpli fi ed hydrostratigraphic map of the alluvial fan Ca 2 + ,

Fig. 4

Simpli ed hydrostratigraphic map of the alluvial fan

Ca 2+ , Mg 2+ were measured by inductively coupled plasma (ICP) with analytical precision of ±0.01 mg/l; and HCO

was measured by titration with analytical precision of tremendous quantity of atmospheric tritium. The nal year

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- sponding to that time. Using this peak, one can get the mean residence time and inltration rate of water. In Denmark, Andersen and Sevel ( 1974) have shown that the measured tritium pro le in groundwater is the reverse of the classic curve for tritium in precipitation. In general terms, consider that there is a parcel of groundwater in a regional aquifer. The composite of several years precipitation have contributed to ground- water through mixing in the unsaturated zone. In this process, tritium content in groundwater will decrease by decay. The tritium concentration in this groundwater parcel will be a function of its residence time in the recharge environment. The exponential model of tritium concentration is predicted by

d 18 O ðd DÞ¼

18 O and deuterium (D) abundances are expressed as ratios in delta notation ( δ) as per mil differences relative to the standard known as the Vienna Standard Mean Ocean Water (VSMOW). They are dened as follows:

Stable isotope analysis

±0.02 mg/l.

12.43 years (Unterweger et al. 1980). Atmospheric testing

of nuclear devices between 1952 and 1962 generated a

3

R

sp

R

st

1 1000

ð1Þ

Where R and R st are the ratios for D/ 1 H or 18 O/ 16 O in the sample or standard respectively. δ 18 O and δ D were analyzed by a Delta S mass spectrometer with analytical precision of ±0.15 and ±1, respectively.

sp

A tritium profile peak and input function for tritium in groundwater and tritium analysis

Tritium ( 3 H or T) is probably the most commonly employed radioisotope used to identify modern recharge. It is a short-lived isotope of hydrogen with a half-life of

C ðÞ¼t

1

Z

0

C R ðt Þ exp ð Þ

l ¼ 1=T l ¼ In2 =sT h

1

T exp

T

d

ð2Þ

where T h is the half-life of tritium, T is the mean residence time, C R ( t ) is tritium concentration in precipitation, and C ( t) is the recharged tritium concentration. If C R ( t ) can be 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, Chinese Academy of Geological Sciences, Zhengding.

Results

Chemical and isotopic data of samples are shown in Table 1. The depths of the wells sampled are from 8.5 to 150 m (Table 1). Based on vertical distribution of the aquifer mentioned above (Yang et al. 2001; Chen et al.

Table 1 Chemical and isotopic data of samples

2004), the groundwater was separated into a vertical two- layer structure (the upper layer and the lower layer) with a boundary at 80 100 m depth.

Geochemical characteristics of groundwater and surface water

Ion concentrations in the two layers were different

(Table 2). Cl , Ca 2+ and NO

higher in the upper layer, and HCO

concentrations were higher in the lower layer. Figure 5 shows the relation between the major ion concentrations

, Na + , Ca , K + , Mg 2+ ) and the

depths of the wells in the alluvial fan. The major ions might be divided into three types: one type is Cl , SO

,

(Cl , HCO

3 ion concentrations were

and Na + ion

3

2+

, SO

4

2

3

, SO

2

4

, NO

3

2

4

Sample/

Sample

Well

Ca

2+

Mg 2+

Na +

K

+

HCO

Cl

SO

2

NO

3

δ

18 O

δD

Tritium

3

4

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

8.75

9.27

7.51

66.18 22.23 77.01 18.5 78.57 21.59 64.46 22.02

R2

River

87.82

17.43

13.43

2.52

189.53

17.83

102.37

53.33

R3

River

95.81

20.58

19.54

2.64

195.27

32.1

105.24

72.73

R4

River

87.82

21.79

18.98

2.97

141.28

28.53

138.73

73.94

R5

River

67.86

18.64

9.17

1.72

189.53

15.69

66.97

40.16

8.64

R6

R7

River

River

73.85

72.65

19.37

20.58

21.34

6.52

3.2

1.37

172.3

183.78

19.26

7.85

103.33

74.63

162.65

66.97

147.44 60.97

8.54

150.56 8.66

8.21

35.16

40.97

43.86

8.7

8.4

72.26 21.87 60.49 19.74 73.38 21.05 74.32 23.85 68.09 38.84

59

26.8

G1

G2

G3

GW

GW

GW

8.5

24

25

127.74

95.81

183.12 36.29

27.84

35.10

21.06

22.35

52.98

3.01

1.27

5.32

189.53

344.59

384.40

39.23

44.94

72.20

G4

G5

GW

GW

25

27

127.74

71.86

34.38

21.79

31.58

18.52

2.55

1.53

402.02

195.27

46.37

17.83

17.82

100.46 32.32

116.72

7.05

8.61

72.74 23.51

26.59

68.3

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

62.06 21.22 59.06 15.65 76.83 31.29 78.99 19.07 60.48 21.36 64.3 28.1 65.2 23.5 65.2 25.2 72.71 24.15 66.25 14.75 75.36 22.93 68.82 16.29 59.7 12.2 80.72 11.15 66.4 9.4 68.62 11.89 72.69 7.53

− − 10.56 81.83 10.96

7.18

7.67

8.66

8.82

7.89

8.4

8.6

8.3

8.84

8.52

8.13

9.24

7.5

8.75

8.4

9.3

9.75

8.8

64

1.9

G9

GW

30

57.03

23.59

35.74

7.77

185.50

60.63

57.97

0.00

G10

GW

31

73.85

21.30

14.07

0.91

206.76

28.53

79.41

26.30

G11

GW

34

65.87

9.68

9.92

0.88

212.50

21.40

23.92

12.67

G12

GW

35

101.80

67.78

41.39

1.11

476.69

92.73

81.32

28.99

G13

GW

40

93.81

19.58

15.56

1.55

298.65

32.10

49.75

G14

GW

40

41.00

45.00

29.10

1.11

313.00

34.00

11.00

G15

GW

40

191.54 41.35

25.47

6.15

294.85

53.94

140.79

G16

GW

40

94.00

67.00

41.50

1.89

407.00

62.00

165.00

27.78

G17

GW

40

35.00

42.00

12.40

1.95

315.00

36.00

15.00

0.00

G18

GW

45

95.01

33.89

21.97

1.77

292.90

21.40

108.11

47.81

G19

GW

50

24.27

18.89

60.69

1.52

284.60

1.66

20.16

G20

GW

60

66.46

36.83

22.27

2.72

304.61

57.95

2.69

G21

GW

70

51.10

19.37

16.73

1.32

235.47

32.10

7.65

5.61

G22

GW

80

22.00

39.00

15.90

0.86

263.00

25.00

5.00

G23

GW

80

56.19

13.45

12.80

2.54

216.25

16.47

30.67

G24

G25

GW

GW

80

100

26.38

70.30

16.35

28.98

63.05

14.75

2.66

2.47

294.85

296.80

12.44

31.43

28.66

68.61

G26

GW

110

64.13

29.92

47.77

2.75

269.70

56.20

27.79

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

9.09

8.95

8.86

8.81

8.91

8.8

62.38 17.64 58.95 18.43 64.39 21.54 61.26 22.54 65.37 20.18 81.42 19.42

S2

Spring

89.02

29.05

17.13

2.05

246.96

28.53

120.55

20.80

S3

Spring

59.88

19.37

8.60

1.79

149.32

10.70

95.68

39.21

S4

Spring

49.90

19.37

9.20

1.42

229.73

3.57

28.70

45.18

S5

Spring

71.86

19.37

11.49

4.57

172.30

14.27

74.63

22.25

S6

Spring

87.82

21.79

4.79

1.35

212.50

10.70

79.41

6.09

GW groundwater from wells

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

SO

2

NO

Na +

Ca 2+

K +

Mg 2+

3

4

3

Upper layer

080

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 Ca 2+ , and the third type is NO

3 . The upper layer (080 m) is an unconned layer of ne sand and silt, and all ion concentrations varied widely. The concentrations of Cl , SO , Na + and K + decreased as the well depth increased. Likewise, HCO and Ca 2+ (the second water type) decreased with the well depth in this layer. The lower layer (100150 m) is a conned layer of sand and gravel; depth 80 100 m is the boundary of the upper and the lower layer. Cl , SO , Na+ and K+ ion concentrations increased with the well depth, and there was no signicant increase in and Ca2+ ion concentration with increasing depth. Groundwater in this lower layer is used because of the decline in the water table. Nitrate is the most common water contaminant index for anthropogenic sources (Freeze and Cherry 1979). In

2

4

3

2

4

the upper layer, ion concentration decreased as the well depth increased. However, nitrate was undetectable in the

lower layer. The difference in NO

between the two layers re ects a change in the inuence

of human activities.

ion

concentrations were 3.5744.94 mg/l, 28.7189.44 mg/l, 149.32252.7 mg/l and 6.09 45.18 mg/l respectively.

Na + , Ca 2+ , K + and Mg 2+ ion concentrations were 4.79

27.77 mg/l, 49.9 89.02 mg/l, 1.35 4.57 mg/l and 19.3746 mg/l respectively (Table 1 ). The range of ion concentrations was close to the groundwater in the upper layer, and springs were recharged by groundwater of the upper layer.

ion

concentrations were 3.5732.1 mg/l, 66.97138.73 mg/l,

3 ion distribution

3

and NO

3

In the springs, Cl , SO

2

4

, HCO

In the river water, Cl , SO

2

4

, HCO

3

and NO

3

the river water, Cl − , S O 2 4 , HCO 3 and NO 3

Fig. 5 The distribution of ion concentrations (Cl , HCO indicate the variation area of major ion concentrations

3

, SO

2

4

, NO

3 , Na + , Ca 2+ , K + , Mg 2+ ) versus the depths of the wells. Dashed lines

Fig. 6 The distribution of ion concentration in river water versus east longitude 65.47 –

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

65.47195.27 mg/l and 10.4473.94 mg/l respectively, and showed the highest NO concentration compared with that in the groundwater. Na + , Ca 2+ , K + and Mg 2+ ion concentrations were 4.94 21.34, 31.9495.81, 1.373.2 and 12.1 21.79 mg/l respectively (Table 1). Beisha River ows from west to east in the study area. Na + , Ca 2+ and all anion concentrations increased along river ow direction (Fig. 6).

3

Isotopic characteristics of groundwater and surface water

Stable isotopes of water are excellent tracers for recharge

of surface water to groundwater (Craig et al. 2002).

O

and D are naturally occurring stable isotopes of oxygen and hydrogen, respectively (John et al. 2002). Stable isotopes show different changes between the upper and lower groundwater layers (Fig. 7). In the upper layer, the

δ 18 O and δ D values ranged from 9.75 to 7.05and

18

80.72 to 59respectively. The δ 18 O values decreased

with the well depth, but the change of δD values was not

obvious. In the lower layer, the δ 18 O and δD values ranged from 10.56 to 7.8 and from 81.83 to 63 , respectively. The δ 18 O and δD values decreased with the well depth in this layer. Groundwater in the upper layer had greater δ 18 O than that in the lower layer. The δ O and δD values in the river water ranged from 9.52 to 7.51 and 78.57 to 60.49respectively and showed the lower isotopic values. On the other hand, the δ 18 O and δD values in the spring ranged from 9.09 to 8.8and 81.42 to 58.95, respectively (Table 1).

18

Tritium characteristics of groundwater and surface water

Generally, the tritium contents of groundwater from wells are higher in the upper layer (7.53 38.84 TU) than in the lower layer (less than 11 TU; Table 1). River and spring

lower layer (less than 11 TU; Table 1 ). River and spring Fig. 7 The distribution

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

Fig. 8 Relationship between δ 1 8 O and δ D in the water samples.

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

water shows the higher tritium contents (greater than 17 TU).

Discussion

The source of groundwater and surface water

Because most of the worlds precipitation is derived from evaporation of seawater, the δ O and δD composition of precipitation throughout the world is linearly correlated. This relation is known as the global meteoric water line (GMWL) and expressed as follows (Craig 1961 ):

d D ¼ 8 d 18 O þ 10 .

The δ 18 O and δD composition of all water samples in the study region were plotted to the right of the global meteoric water line (GMWL; Fig. 8 ). From the relation- ship shown in Fig. 8 , all of the points in the upper groundwater layer were under the GMWL and the linear relationship is approximately parallel to the GMWL, showing that groundwater of study area has been recharged by precipitation and these samples have not

18

been subjected to signicant evaporation during inltra- tion into the aquifer. The intercept is often referred to as the deuterium-excess (d-excess), de ned as d ¼ d D 8 d 18 O (Dansgaard 1964). The d-excess is a useful proxy for identifying secondary processes in uencing the atmo- spheric vapor content in the evaporation-condensation cycle in nature (Craig 1961; Merlivat and Jouzel 1979).

The d-excess values of groundwater samples ranged from

10 to 10in the upper layer and from 0 to 10in the lower layer (Fig. 8 ). It can be considered that the groundwater originates from rainfall with different d- excess values. On the other hand, based on hydrology and human activities, the upper ow system has been affected by many phenomena such as (1) location of Hutuo River in the center of the alluvial fan plain, (2) excess irrigation water return ow to the aquifer. According to the study of Zhang et al. (2000), a δ 18 O value of less than 9signies groundwater older than 10,000 years in the NCP because the climate became warm 10,000 years ago. Whereas, if the groundwater is younger than 10,000 years, the δ 18 O value would be

younger than 10,000 years, the δ 1 8 O value would be Fig. 9 Relationship between

Fig. 9 Relationship between δ 18 O and tritium in the water samples

Fig. 10 The distribution of tritium versus the depths of the wells. Dashed lines indicate

Fig. 10 The distribution of tritium versus the depths of the wells. Dashed lines indicate the variation area

greater than 9. In the upper layer, δ 18 O values of samples were higher than 9except G19, G23 and G24; in the lower layer, δ 18 O value of G29 and G26 was higher than 9, and the others were lower than 9(Fig. 9). It can be considered that groundwater in the upper layer and groundwater of G29 and G26 in the lower layer was younger than 10,000 years (modern water) in the alluvial fans. In the NCP, the tritium value of rainfall that is older than 10,000 years is considered to be close to 0 TU, so the groundwater in the lower layer is a mixture of new water and old water. Almost all river water and spring water is younger than 10,000 years, except R1, R3 and S6. Tritium values of R1, R3 and S6 were higher than

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 δ 18 O 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 ow 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 in uences the shallow groundwater in the middle and the littoral plain and not the deep conned aquifers (Chen et al. 2003). The tritium concentrations in river water and groundwater had a strong exponential dependence relation to well depth in the upper layer (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 than 15 TU. On the basis of data from the International Atomic Energy Agency (IAEA), the distribution graph of tritium concentration in global meteoric water can be described. Based on tritium values of river water in Fig. 10, tritium concentration of rainfall in the NCP was 18 22 TU. In addition, modern water (groundwater in the upper layer; Fig. 9) was supplied by modern rainfall. In this study, it is considered that groundwater is recharged from rainfall and the peak value of tritium contents is due to the atmospheric testing of thermonuclear bombs between 1952 and 1962. Using the model described in Eq. ( 2) the tritium input can be determined on the basis of measured

the tritium input can be determined on the basis of measured Fig. 11 Tritium distribution in

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

Fig. 12 The vertical distribution of δ 1 8 O ( ‰ ) in groundwater

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

tritium data. From the model, it can be considered that the vertical velocity of groundwater in the upper layer is less than 1 m/year.

tritium concentration. By the exponential model, it can be calculated that horizontal ow velocity is faster than 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

the ow direction of groundwater in the lower layer is from west to east, so tritium contents decrease with the

horizontal distribution (along OO` in Fig. 2) reached a peak at about 114.5° E (Fig. 11a). As mentioned above, an

exponential model can be educed from the distribution of groundwater ow.

can be educed from the distribution of groundwater fl ow. Fig. 13 Piper diagram for the

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

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

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

Spatial evolvement characteristics of stable isotopes and chemical composition

Because the groundwater level is higher in the mountain- ous areas, groundwater constantly ows into the plain, and the mountainous area plays an important role as a recharge 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 aquifer by inltration. Because it inltrates into the aquifer directly, evaporation and oxygen isotope shift have less inuence on it. The δ 18 O values of the groundwater in some places (e.g. G19, G23 and G24) were low compared with most places in the upper layer (Fig. 12). This implied that the irrigation has an inuence on the aquifer. There are a lot of irrigation wells in the alluvial fan plain leading to excessive groundwater use as well as irrigation return (water returned to the aquifer after use). The Piper diagram (Piper 1944) is the most widely used graphical form to express geochemistry results and it is quite similar to the diagram proposed by Hill ( 1940). The diagram displays the relative concentrations of the major cations and anions on two separate trilinear plots (Güler et al. 2002). The points of the central diamond are from the two trilinear plots (Güler et al. 2002). The central diamond-shaped eld is used to show overall chemical character of the water (Hill 1940; Piper 1944). Figure 13 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 of Na + and Cl and the type was HCO 3 NO 3 Ca. Because of the effect of carbonate rock and metamorphic rock in the mountains region (Fig. 4), groundwater in the upper layer was characterized by CaHCO 3 . On the other hand, groundwater points in the lower layer were broadly distributed rather than forming distinct clusters. Ground- water in the lower layer was classi ed into two dominant water types: HCO 3 CaMg and HCO 3 NaK. In the discharge area, groundwater was characterized by NaHCO 3 type (Fig. 14). Formation of this chemical

type is probably related to ion exchange between groundwater and groundwat er that is mainly excess irrigation return. Every time the return water re-percolates through the soil pro le, it dissolves more salts, resulting in the mixed chemistry as shown in Fig. 14.

Protection of the groundwater resource

The NCP is one of the most important agricultural areas in China. Groundwater storage and quality are affected by agricultural irrigation and industrial development. Because the agricultural irrigation water and some industrial and domestic use water come from aquifers, the groundwater level has a downward trend and water quality is getting

worse. NO

3 concentrations from about 18% of water

samples were higher than the water quality standard for drinking water sources (NO : 44 mg/l; Ministry of Health of the Peoples Republic of China 2006; Table 1). The authors herein suggest that management of the groundwa- ter resource includes three points. Firstly, irrigation management should be carried out under scienti c direction; good planning of irrigation in dry years is especially important for saving water (Yang et al. 2006). Secondly, the management system of industrial and city water use should be optimized; and thirdly, the monitoring of wastewater discharge and disposal should be intensied.

3

Conclusions

In this study, water quality, stable isotopes and tritium were used to determine the groundwater ow path. The main ndings can be summarized as follows:

1. The δ 18 O and δ D values ranged from 10.56 to 7.05 and 81.83 to 59 respectively. The groundwater in the upper layer originates from rainfall with different d-excess values, and has not been subjected to signi cant evaporation during inltration

into the aquifers. Groundwater in the upper layer is younger than 10,000 years.

2. Groundwater ow velocity can be determined using a tritium model, but a tritium exponential model cannot be used to identify age of old water. In the alluvial fan plain, the groundwater ow velocity is in the order:

horizontal ow velocity > vertical velocity. Vertical velocity is <1 m/year.

3. Irrigation has an in uence on the aquifer. The distribution of δ 18 O along a cross section from west to east (O O) could imply that water was withdrawn from the aquifer for irrigation, and then returned to the aquifer after use.

4. Because of the effect of carbonate rock and metamor- phic rock in the mountains region groundwater in the upper layer is characterized by Ca HCO 3 type. Formation of NaHCO 3 type in the discharge area is probably related to ion exchange between groundwater and recycled groundwater that is mainly excess irrigation water return.

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