Journal of Geochemical Exploration 136 (2014) 2439

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/jgeoexp

Evaluation of the impact of an uncontrolled landll on surrounding

groundwater quality, Zhoukou, China
Dongmei Han a,, Xiaoxia Tong b, Matthew J. Currell c, Guoliang Cao d, Menggui Jin e, Changshui Tong e
a

Key Laboratory of Water Cycle & Related Land Surface Processes, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing 100101, China
School of Water Resources and Environment, China University of Geosciences, Beijing 100083, China
School of Civil, Environmental and Chemical Engineering, RMIT University, Melbourne, Australia
d
Center for Water Research, College of Engineering, Peking University, Beijing 100871, China
e
School of Environmental Studies, China University of Geosciences, Wuhan 430074, China
b
c

a r t i c l e

i n f o

Article history:
Received 1 April 2012
Accepted 30 September 2013
Available online 9 October 2013
Keywords:
Uncontrolled landll
Inorganic contamination
Groundwater hydrochemistry
Groundwater quality
Contaminant transport model

a b s t r a c t
Our groundwater pollution investigation of an uncontrolled municipal landll aims to better understand the possible impact of leachate percolation on groundwater quality. The study examined groundwater inorganic contamination around a municipal landll site in Zhoukou city, Henan province, China. Stable isotopic compositions (18O and
2H) and concentrations of various physico-chemical parameters were determined in surface and groundwater
samples collected from the study area. 18O and 2H compositions reveal that elevation effects and/or evaporative
processes occur to various extents prior to water reaching the saturated zone. There is no serious heavy metal
contamination in this area. Principal component analysis was applied, and identied TDS, Cl, NH+
4 , Fe and Mn
concentrations as the main indicators of groundwater pollution caused by landll leachate percolation. The groundwater quality of shallow aquifer is likely dominated by irrigation return ow in the summer. A two-dimensional
advectivedispersive transport model was established using MODFLOW and MT3DMS to explore the controls on
contaminant transport. Chloride transport simulations with steady state and transient ow models show that the
contamination plume is still constrained in the upper aquifer after 13 years of operation of the landll. The contrast
between the simulated (relatively short) migration distance of the chloride plume, and the widely observed high
chloride concentrations in the upper aquifer indicate other possible local contributions to the salinity of the aquifer.
The transient model indicates that seasonal dynamics, such as temporal water level variations, may have a great inuence on the migration of the plume beneath the landll by controlling vertical hydraulic gradients and uxes. In
general, the shallow groundwater (within 30 m depth) around the Zhoukou landll is not suitable for drinking, and
pollution control should be improved and enhanced in this area.
2013 Elsevier B.V. All rights reserved.

1. Introduction
The common landll receives a mixture of municipal, commercial and mixed industrial waste, typically producing a wide range
of pollutant compounds with resulting environmental, wildlife and
human health impacts. A large number of landll-caused groundwater pollution cases have been reported around the world (AbuRukah and Al-Kofahi, 2001; Arneth et al., 1989; Christensen et al.,
1998; Flyhammar, 1995; Looser et al., 1999; Rapti-Caputo and
Vaccaro, 2006; Saarela, 2003), and substantial resources spent on
groundwater remediation in these areas suggest that landll

Corresponding author.
E-mail address: dmeihan@gmail.com (D. Han).
0375-6742/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.gexplo.2013.09.008

leachates, generated by excess rainfall percolating through waste

dump, are signicant sources of groundwater pollution and pose major
risks to groundwater quality (Christensen et al., 2001; Niininen et al.,
1994). To date, there are few studies investigating the extent and mechanisms of groundwater contamination in China. This is despite the fact that
it is known that contamination is almost ubiquitous in most urban areas,
and that the nation faces a potential public health crisis due to groundwater pollution (Li, 2013).
Many industries dispose off waste chemicals by placing them in unlined soil pits and lagoons, where they can easily migrate to surface and
groundwater. Physical, chemical, and microbial processes within the
waste can be combined to transfer pollutants from the waste material
into percolating rainwater. Furthermore, it has been shown that heavy
metals (e.g. Cd, Cu, As, Pb, and Cr6+), ammonium (NH+
4 ), and nitrate
(NO
3 ) from uncontrolled landlls pose a major threat to human health
through ingestion of contaminated groundwater (Lee et al., 2006). Multiple indicators, including major hydrochemistry, and stable isotopes of

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

water (18O, 2H), have been used to provide an improved understanding

of the complex hydraulic and hydrological conditions present in urban
areas (Barrett et al., 1999; Foster, 1998; Morris et al., 2006; Osenbrck
et al., 2007).
Of the seven large rivers in China, the Huaihe River has the highest
population density and the most serious water contamination issues
(Cui and Fu, 1998). With rapid economic development in many cities
of the Huaihe River Basin, increasing demand for water is conicting
with water resource shortages, severely restricting the sustainable utilization of the region's water and the development of many local economies.

25

Zhoukou city is located in the southeast valley of the Huaihe River Basin,
in the conuence of the Ying and the Jialu Rivers, which belong to tributaries of the Huaihe River (Fig. 1). Groundwater is the main source of
water supply for industrial, agricultural and domestic use in Zhoukou
city (Zhao et al., 2010) and both urban industrial and domestic waste
and sewage discharge to surface water and groundwater. Groundwater
quality around Zhoukou city has been deteriorating rapidly over the last
few decades. Drinking ungraded water and contaminated groundwater
long term can result in endemic diseases. Identication of the sources of
contamination and understanding the pathways of contaminants to and

Fig. 1. Study area and location of sampling sites around the Zhoukou landll. LEGEND: 1residential area; 2landll; 3waters; 4groundwater monitoring wells (sampling wells with
labels in Table 1); 5Surface water sampling sites; 6shallow groundwater table contours (m a.s.l) from the monitoring data in December 2009; 7major groundwater-ow direction;
8ow direction of surface water.

26

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

within the aquifers are essential for accurate prediction of water quality
and for appropriate management of the water resources in Zhoukou city.
The present study undertook hydrogeological and hydrochemical
isotopic monitoring of the shallow aquifers underneath and around
the Zhoukou uncontrolled landll, Henan province, in order to: (i) investigate the distribution of inorganic macrocomponents and minor elements (including heavy metals) in surface and groundwater around the
Zhoukou landll, (ii) better understand the possible impact of leachate
percolation on groundwater quality and evaluate the potential sources
of inorganic pollutants and the extent of the contamination, (iii) study
the spatial characteristics of the area impacted by the landll, and relate
this to the site's hydraulic properties (iv) assess groundwater quality
and put forward some remedial measures for reducing further groundwater contamination. The research results provide a scientic foundation for
protecting and managing groundwater resources in Zhoukou and similar
areas, and we hope provides a good example for further groundwater
contamination research in China in the coming years.

2. Materials and methods

2.1. Study area
The study area is located in the north of Zhoukou city, between longitudes 11434 and 11443 E and latitudes 3333 and 3343 N
(Fig. 1), occupying a total area of 18 km2. The study area borders the
Ludong Trunk Canal to the north, the Ying River to the south, the Jialu
River to the west, and the Low-lying Gully to the east. The elevation of
the study area ranges from 45 to 51 m above mean sea level, with a
mean land surface slope of 0.2 from southeast to northwest. The
length of the landll site measures 200 m from south to north, and
90 m from east to west and is currently surrounded by the city planning
area. Hydrogeological bore logs can be seen in Fig. 2, showing the major
geological layers in the vicinity of the landll. At the center of the landll
(ZKC in Fig. 2), the waste layer composed of domestic waste is 9.3 m
thick. Around the landll, the shallow aquifer is within 30 m below

the ground surface, with a thickness of 523.7 m and a hydraulic conductivity of 1.218.1 m/d. One deeper aquifer exists at a depth of 45
52 m, with a hydraulic conductivity of 1216 m/d (Qu, 2010). These
aquifers consist of inter-bedded ne sand and silty sand. The landll
has been accepting municipal solid waste from the City of Zhoukou
since 1998 and was closed in 2010. The accumulative amount of solid
waste reached approximately 13 104 m3. A sewage ditch is located
to the east of the landll, where the long-term leaching of waste and
sewage discharge has had a serious impact on ambient groundwater
quality.
The climate in this region is a continental monsoonal type, with an
average annual potential evapotranspiration (PET) (annual mean
water surface evaporation) of 1736 mm and an annual precipitation of
728 mm (Xie, 2011). Over 60% of total precipitation occurs in the wet
season (JulySeptember). The Ying and the Jialu Rivers in the study
area both belong to the Huaihe River Basin and are perennial rivers,
fed by baseow at most times of the year. In 2005, the total yearly
groundwater extraction had reached 1163.3 106 m3 for the whole of
Zhoukou city, which covers an area of 214 km2. Shallow groundwater
extraction, which is mainly used for irrigation and rural drinking
water, accounts for about 90% of the total groundwater exploitation
(Qu, 2010). Deep groundwater exploitation is mainly used for urban
living and industrial utilization. This study focuses on investigating
groundwater chemistry of the shallow aquifer within 1325 m depth.

2.2. Sampling and analysis

Based on prior analysis of the geologic, tectonic and hydrogeological
conditions of the Yangwu River alluvial fan, 48 sampling sites, including
41 groundwater and 7 surface water sites, were chosen for analysis and
samples were collected in December 2008, May 2009, December 2009
and June 2010. The locations of the sampling stations are shown in
Fig. 1. Surface water samples were collected from a sampling depth of
0.5m below the surface. Groundwater samples were collected from production wells at a range of depths (9300 m).

Fig. 2. Typical hydrogeological bores of the Zhoukou landll for monitoring water level. ZKC and ZKS are located at the center and some 150 m south of the landll, respectively. The
hydraulic parameters of the aquifers are referenced from the results of pumping tests (Tong, 2012).

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

27

Table 1
Physico-chemical parameters of water samples around the landll.
ID

Sampling time

Well
depth
(m)

Well
screen
(m)

Utilization

T
(C)

pH

EC
(S/cm)

Eh
(mV)

DO

Ca2+

Mg2+

Na+

K+

Al

Fe

Mn

ZA
ZB
ZC
ZD
ZE
ZF
ZG
Z6
Z6A
SW29
SW49
SW59
ZK1
ZKE
ZKW
ZKS
ZKN
ZF
DW09
DW18
DW23
DW25
ZG10
ZG11
ZG12
Z16
Z34
Z40
ZC
SUJL
SULG
SUY
SULD
ZKE
ZKW
ZKS
ZKN
ZB
ZG9
Z06
Z40
Z16
ZF
DW09
Z34
DW25
SUJL
ZC
ZKE
ZKS
ZKW
ZKN

Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
Dec.2008
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May 2009
May.2009
May 2009
May 2009
May 2009
May 2009
May.2009
May 2009
May 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Dec. 2009
Jun. 2010
Jun. 2010
Jun. 2010
Jun. 2010

30
50

18
20
20
16
9
14
6
300
27
27
27
27
18
16
30
18
30
9
9
9
30
28
30

27
27
27
27
50
9
15
30
30
18
16
28
30

27
27
27
27

13.025.2
12.625.1

Agricultural irrigation
Domestic well
Sewage water
Water from pond
Waste leachate
Agricultural irrigation
Domestic well
Domestic well
Domestic well
Domestic well
Domestic well
Domestic well
Urban water supply
Observation well
Observation well
Observation well
Observation well
Agricultural irrigation
Domestic well
Domestic well
Domestic well
Domestic well
Observation well
Observation well
Observation well
Agricultural irrigation
Agricultural irrigation
Agricultural irrigation
Sewage water
River water
Sewage water
River water
Agricultural irrigation
Observation well
Observation well
Observation well
Observation well
Domestic well
Observation well
Agricultural irrigation
Agricultural irrigation
Agricultural irrigation
Agricultural irrigation
Domestic well
Agricultural irrigation
Domestic well
River water
Sewage water
Observation well
Observation well
Observation well
Observation well

16.6
14.6
19.6
13.9
11.1
16.8
17.3
17
17
16.3
18.3
17.5
22

7.71
7.7
7.7
8.14
7.93
7.27
7.3
7.3
7.09
7.49
6.96
7.5
8.47

964
1086
1602
638
3255
3365
2235
1770
1734
1255
1231
1325
893

256
195
208
138
184
328
283
160
149
60
137
5
72

6.38
5.46
4.03
3.06
5.76
1.54
4.97
8.67
5.59
6.10
0.48
0.54
2.41

18.3
18.4
19.3
17.6
18.9
21.5
18.4
20.5
18.9
18.7

8.94
7.48
6.89
7.63
7.39
7.97
7.52
7.5
7.46
6.83

396
961
3644
1316
1369
2930
1671
1332
1076

98
3
115
151
153
106
198
171
73
25

1.07
1.98
1.92
2.55
1.85
2.05
2.06
2.13
2.29
2.29

17.6
17.2

7.62
7.61

1809
1162

194
189

2.35
1.98

17.8
16.6
17.5
18.4
10.1
18.5
16.8
16.5
17.4
16.1
15.8
15.6
7.6

7.29
7.21
7.43
6.61
7.63
7.39
7.25
7.33
7.73
7.42
7.02
7.19
7.59

1676
1652
1353
3999
1164
1219
1378
1494
787
1502
1726
1985
1412

91.3

122
30.0
69.1
44
178
259
218
159
1.55
80.8
275.6
124.2
28.5
51.7
33.2
32.6
128
76.8
90.7
16.6
74.7
59.5
58.1
67.8
64.6
65.3
123
69
69.1
72.6
39.8
74.9
81.3
161.0
193.6
92.0
397.6
104.0
73.0
172.9
158.7
102.4
134.9
162.7
175.4
119.0
92.8
81.0
159.5
103.4
227.7
327.1

45.2
57.6
35.9
27.4
95.4
68.7
68.8
63.1
58.7
39.4
83.5
49.0
18.2
65.1
17.5
35.9
210
81.6
110
46.7
102
85.5
37.8
45.5
13.7
71.3
96.3
73.5
32.9
32.2
30.2
37.6
53.1
55.3
75.6
37.5
212.6
61.1
30.3
47.1
57.7
27.9
54.0
80.8
102.9
67.8
29.4
28.9
71.0
35.5
101.6
174.0

30.2
68.8
179
62
206
125
114
81.4
103.6
111.2
106.8
93.0
148.5
225.0
93.4
220
369
196
169
255
184
198
234
872
580
158
202
185
202
174
179
182
175
161.0
61.0
150.0
346.0
72.8
144.5
38.8
76.5
34.3
119.5
90.0
105.0
111.0
92.0
168.0
189.4
151.5
80.5
321.3

6.5
0.7
16.9
6.9
105
3
3.6
25.8
91.1
0.4
27.6
0.1
1.2
3.1
11.9
11.2
55
6.1
41.6
4.1
0.5
0.6
0.3
12.8
2
1.4
0.6
9.3
8.6
10.6
9.8
10.7
6.6
1.1
8.4
3.1
61.6
0.9
0.5
3.6
1.9
8.6
9.7
40.3
0.4
0.5
10.0
14.2
1.7
2.1
7.7
51.2

0.07
0.02
0.3
0.3
0.1
1.1
0.9
0.1
0.01
0.01
0.07
0.2
0.01
0.02
0.32
0.14
0.07
0.01
0.01
0.01
0.01
0.01
0.05
0.01
0.01
0.01
0.01
0.03
0.02
0.05
0.01
0.24
0.15
0.6
0.42
0.82
0.05
0.02
1.1
0.02
0.1
0.8
0.14
0.02
0.02
0.02
0.11
0.02
0.17
0.13
0.04
0.02

0.2
0.05
0.4
0.5
0.3
1.1
0.8
0.7
0.01
0.06
0.3
0.2
0.01
0.05
0.19
0.08
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.08
0.05
0.05
0.15
0.23
9.3
1.1
11.1
1.8
0.1
8.6
0.2
0.4
4.8
0.8
0.2
0.3
0.3
0.4
0.4
2.7
4.0
0.7
1.3

0.33
0.07
0.11
0.13
0.32
0.17
0.05
0.53
0.31
0.09
0.01
0.45
0.04
1.04
0.02
0.24
0.67
0.16
0.33
0.1
0.09
0.01
2.63
0.58
0.66
0.02
0.32
0.18
0.16
0.01
0.01
0.01
0.29
3.92
0.73
2.98
1.46
0.14
1.7
0.6
0.15
1.35
0.56
0.27
0.28
0.24
0.01
0.11
2.1
1.4
0.24
0.68

13.224.5
12.222.0
13.024.0
12.823.6
5.29.0
7.513.8
4.26.0
11.722.8
12.625.3
11.225.1
13.724.1
13.224.5
9.215.9
11.228.8
7.617.8
8.225.7
4.58.8
4.89.0
5.28.9
14.525.1
12.822.5
13.226.3

11.722.8
12.625.3
11.225.1
13.724.1
12.625.1
4.39.0
7.514.6
13.226.3
14.525.1
13.224.5
9.215.9
12.822.5
8.225.7

11.722.8
11.225.1
12.625.3
13.724.1

87.2
50.7

Hg
As
Se
NH4+ H2SiO3 CODMn Cl
Cd
Pb
Zn
Cr6+
(g/L) (g/L) (g/L) (g/L) (g/L) (g/L) (g/L)

ID

Sampling
time

ZA
ZB
ZC
ZD
ZE
ZF
ZG
Z6
Z6A
SW29
SW49
SW59
ZK1
ZKE
ZKW
ZKS
ZKN
ZF

Dec. 2008
0.9
Dec. 2008
1.2
Dec. 2008
2.0
Dec. 2008
1.0
Dec. 2008
2.6
Dec. 2008
2.7
Dec. 2008
2.2
Dec. 2008
2.2
Dec. 2008
4.0
Dec. 2008
3.6
Dec. 2008
4.4
Dec. 2008 b0.1
Dec. 2008
4.0
May 2009
1.1
May 2009
0.4
May 2009
0.6
May 2009
1.0
May 2009
0.7

2
3
2
2
3
4
2
2
13
8
16
15
2
4
3
4
4
3

11
2
87
22
29
18
41
30
30
30
37
30
5
5
3
2
3
1

b4
b4
b4
32
b4
b4
b4
b4
5
5
5
5
5
b4
7
7
b4
b4

0.1
0.1
b0.1
b0.1
b0.1
0.1
0.1
3.9
0.6
8.2
b0.1
3.7
1.7
b0.1
0.2
b0.1
b0.1
b0.1

1
1
b1.0
1.9
10.6
1.1
1
b0.1
b0.1
b0.1
b0.1
b0.1
b0.1
4.4
3.2
23.9
3
0.9

0.2
0.2
b0.2
b0.2
b0.2
0.2
0.2
0.2
b0.1
b0.1
7.2
b0.1
b0.1
1.4
1.4
0.9
0.8
1.2

0.17
0.03
47.9
0.25
141
0.02
0.02
0.22
b0.02
b0.02
b0.02
b0.02
b0.02
0.45
0.33
0.99
0.02
0.13

20.1
20.1

28.6
20.9
21.9
29.8
20.4
20.1
11.2
31.2
26.6
24.4
24.7
27.7
23.3

0.52
0.76
13.41
6.97
40.31
1.47
0.68
1.15
1.7
1.8
1.8
1.5
2.3
3.5
3.9
7.2
1.6

55.9
62.2
153.0
53.9
328.0
140.0
115.0
151.0
202.8
56.4
246.7
126.9
104.2
164.0
51.2
122.0
976.0
138.0

SO2
4

HCO
NO
3
3

46.9
89.8
120.0
52.8
380.0
277.0
155.0
66.0
58.3
79.8
126.0
300.0
73.5
147.0
143.0
137.0
149.0
331.0

506.0
315.0
631.0
274.0
656.0
777.0
698.0
720.0
521.1
569.3
660.2
297.2
314.9
691.0
179.0
478.0
599.0
644.0

NO
2

Hardness TDS
(g/L)

2.4
0.63
0.004
0.10
492
0.2
1.11
0.004
0.06
312
b0.2
0.77
0.014
0.09
321
b0.2
0.86
0.040
0.02
224
b0.2
0.49
0.013
0.10
838
126
0.43
0.480
0.01
932
260
0.41
0.004
0.02
829
0.2 b0.10 b0.004
0.11
659
1.3
0.33
0.005
0.20
634
5.8
0.56
0.005
0.11
363.8
294
0.46
0.044
0.01 1032
0.4
0.92
0.005
0.19
511.9
0.1
0.45
0.005
0.01
142.1
b0.2
1.33
0.082
0.02
399
15.9
1.16
1.980 b0.01
155
24.4
1.83
0.730
0.02
230
b0.2 b0.02
0.012
1.02 1188
110.0
2.25
0.013 b0.01
680

0.56
0.47
0.89
0.39
1.62
1.39
1.28
0.91
0.78
0.66
1.49
0.84
0.53
1.00
0.46
0.82
2.19
1.26

(continued on next page)

28

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

Table 1 (continued)
Cd
Pb
Zn
Cr6+ Hg
As
Se
NH4+ H2SiO3 CODMn Cl
(g/L) (g/L) (g/L) (g/L) (g/L) (g/L) (g/L)

ID

Sampling
time

DW09
DW18
DW23
DW25
ZG10
ZG11
ZG12
Z16
Z34
ZC
SUJL
SULG
SUY
SULD
ZKE
ZKW
ZKS
ZKN
ZB
ZG9
Z06
Z40
Z16
ZF
DW09
Z34
DW25
SUJL
ZC
ZKE
ZKS
ZKW
ZKN

May 2009
0.6
May 2009
1.2
May 2009
0.8
May 2009
0.7
May 2009
0.6
May 2009
0.7
May 2009
0.7
May 2009
0.7
May 2009
0.7
May 2009
0.6
May 2009
0.5
May 2009
0.5
May 2009
0.6
May 2009
0.7
Dec. 2009
1.8
Dec. 2009
0.6
Dec. 2009
0.6
Dec. 2009
8.2
Dec. 2009
0.6
Dec. 2009
0.6
Dec. 2009
0.7
Dec. 2009 b0.1
Dec. 2009
0.8
Dec. 2009
0.3
Dec. 2009
0.5
Dec. 2009
0.5
Dec. 2009
0.7
Dec. 2009
0.1
Dec. 2009
0.3
Jun. 2010
0.8
Jun. 2010
0.1
Jun. 2010
0.6
Jun. 2010
3.1

3
5
3
6
6
5
3
4
5
5
6
4
6
5
12
3
11
38
2
8
2
2
2
3
2
2
3
1
3
2.1
1.1
3.7
14

1
1
1
4
9
6
4
1
3
16
2
3
3
6
36
10
24
65
b1
26
3
b1
20
b1
1
2
30
1
32
7.4
4.3
1.0
9.6

b4
14
b4
5
b4
22
5
4
5
8
15
7
8
18
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
b4
b4
b4
b4

b0.1
b0.1
0.2
0.2
0.2
b0.1
0.1
0.2
b0.1
b0.1
b0.1
0.1
b0.1
b0.1
0.05
0.01
0.05
0.03
0.1
b0.1
b0.1
b0.1
0.04
0.01
0.04
0.03
0.01
0.04
0.08
0.01
0.08
0.02
0.03

1
7.6
1
1
14.9
4.8
b1
b1
b1
1.1
4.5
8.1
4.9
7.1
8.0
3.6
52.0
6.4
1.7
7.1
0.2
0.5
11
1.5
0.8
0.9
2.4
2.4
0.4
14
24
0.9
1.9

1.8
1.3
1.6
0.9
2.1
1.4
1.6
2.0
0.9
1.2
1.9
1.9
2
2
0.2
0.2
0.2
0.7
0.2
0.1
0.4
0.3
0.2
0.1
0.5
0.1
0.1
1.5
0.4

0.14
0.21
0.04
0.06
0.55
75.6
b0.02
0.11
0.08
45.6
0.11
0.32
0.4
16.4
0.36
b0.02
0.07
0.04
0.4
0.06
0.02
0.02
1.39
0.4
0.02
0.02
0.02
0.07
0.32

19.3
13.4
21.1
19.3
23.7
14.6
32.2
17.3
20.2
17.6
10.6
b2.0
12.2
15.1
25.6
30.1
30.4
25.3
22.7
19.1
22.7
23.2
20.9
25.1
20.3
24.0
19.4
17.0
20.9
25.2
26.5
31.2
39.1

1
3.2
1.4
1.3
2.3
46.7
11.4
1.0
2.0
11.9
6
7.2
6
7
1.0
1.3
2.0
1.0
2.0
0.9
1.2
5.0
9.6
2.2
0.4
1.0
0.1
4.0
19.0
4.3
2.9
1.0
10.3

187.0
249.0
81.5
178
1159
615.0
140.0
244.0
200.0
118.0
136.0
131.0
146.0
155.0
154.2
110.6
136.8
1003.0
82.2
143.6
48.9
126.2
38.6
108.8
110.6
164.8
68.4
108.8
150.7
209.6
118.1
138.1
716.9

NO
2

SO2
HCO
4
3

NO
3

515.0 771.0
225.0 424.0
279.0 604.0
140.0 548.0
203.0 521.1
249.0 995.0
242.0 357.0
445.0 342.0
222.0 484.0
292.0 650.0
220.0 293.0
207.0 227.0
254.0 305.0
184.0 526.0
75.0 782.9
131.0 713.3
39.8 630.9
32.4 1578
85.5 599.8
12.5 536.4
52.0 549.2
104.0 605.9
54.5 429.0
72.0 745.0
177.0 719.4
224.0 688.3
149.0 612.0
126.0 328.3
88.0 289.8
145.8 813.4
47.8 637.8
167.0 860.2
97.8 1358.0

487
4.19 0.680
0.01 234
101
2.59 1.790 b0.01 608
85.5
2.50 b0.004 b0.01 501
b0.2
1.63 b0.004
0.08 305
b0.2 b0.02 0.008
1.81 2045
b0.2
2.30 b0.004
1.59 725
43.6
1.83 0.005 b0.01 457
156
1.58 0.005 b0.01 705
34.6
1.91 1.570
0.01 475
b0.2
2.35 0.012
0.09 528
20.1
0.98 4.450
0.05 314
b0.2
1.48 0.043
0.13 224
42.9
2.63 6.990
0.04 342
41.2
2.66 0.006
0.30 423
0.84 0.29 0.018
0.10 568.4
85.0
0.21 0.077
0.02 792.6
0.1
0.38 0.022
0.16 168.6
3.7
0.38 0.026
0.01 1870
0.6
0.69 0.030
0.07 515.4
0.7
0.41 0.024 b0.01 309.2
195.0
0.39 0.016
0.01 628
51.0
0.38 0.012
0.04 634
1.7
0.46 0.118 b0.01 368.3
0.9
0.47 0.011 b0.01 556.9
70.6
0.30 0.106
0.01 741.1
86.0
0.45 0.008
0.01 860.2
93.5
0.06 0.003
0.06 578.5
19.8
0.58 0.170
0.03 356.8
12.1
0.46 0.101
0.20 321.2
0.8
0.43 0.034
0.11 612.5
0.7
0.50 0.058
0.11 404.3
125.5
0.31 0.105 b0.01 712.7
10.8
0.27 0.030
0.68 1521

Hardness TDS
(g/L)
1.99
1.11
1.11
0.94
0.91
2.36
1.27
1.31
1.12
1.05
0.81
0.71
0.90
0.96
1.00
1.02
0.78
2.85
0.71
0.67
0.83
0.88
0.48
0.87
1.09
1.20
0.92
0.64
0.69
1.18
0.78
1.28
2.38

All in mg/L (if not specied otherwise) except pH.

The wells were purged before sampling and groundwater was collected by pumping, only after constant values of electrical conductivity
(EC) and redox potential (Eh) had been established. Most selected sampling points for groundwater were situated near the landll. A fresh
sample tube was used for each piezometer to prevent cross contamination. Water table depth, pH, turbidity, EC, Eh, dissolved oxygen (DO)
and temperature were all measured in the eld. pH and temperature
were measured at the time of sampling. All samples were ltered
through a b 0.45 m membrane lter to separate the particulate from
the dissolved fraction. In most cases alkalinity was determined on ltered samples in the eld, by titration with H2SO4 (0.22 N). Samples
for major anion analysis were collected in polyethylene bottles,
tightly capped and stored at 4 C until analysis. Samples for cation
analysis were preserved in acid-washed polyethylene bottles, and
acidied to pH b 2 with 6 N HNO3. Major anions (Cl, SO24 , NO
3 ,
precision 510%) were measured using ion chromatography (DX120), while major cations (Ca2+, Na+, K+, Mg2+, precision 510%)
and minor/trace elements were analyzed using ICP-MS in the
Environmental Chemistry Laboratory, School of Environmental
Studies, China University of Geosciences. The measured physicochemical values of water samples from the study area can be seen
in Table 1.
Stable isotope values of 18O and 2H were measured by mass spectrometry, with a Finnigan MAT251 after on-line pyrolysis with a Thermo Finnigan TC/EA (Temperature Conversion Elemental Analyzer), in
the State Key Laboratory of Geological Processes and Mineral Resources,
China University of Sciences. The 18O and 2H values were measured
relative to international standards that were calibrated using V-SMOW
(Vienna Standard Mean Ocean Water) and reported in conventional
() notation. The analytical precision for 2H is 1.5 and for 18O
is 0.2. The tested results are shown in Table 2.

3. Results and discussion

3.1. Groundwater ow system
The landll is located on the oodplain of the Jialu River. Alluvial
sediments at the site range in size from coarse gravel to clay, although
medium-grained sand dominates the aquifers. Two alluvial aquifers
are present within 052 m depth. The shallow aquifer consists of ne

Table 2
Isotope composition for water samples around the Zhoukou landll (sampled in
December 2009).
Water sample

Well depth (m)

18O ()

2H ()

ZKE
ZKS
ZKW
ZKN
ZB
ZF
Z16
Z40
Z06
Z34
DW09
DW25
ZG9
ZK1
SW49
ZC
SUJL

27
27
27
27
50
18
30
30
15
28
19
30
9
300
14
Sewage water
Jialu River

7.1
7.2
6.2
2.7
6.6
5.5
3.7
6.1
6.8
6.9
6.0
6.4
7.0
7.5
6.7
6.9
5.5

63
59
51
34
57
53
36
55
60
62
55
58
64
71
59
59
52

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

sand and silty sand at a depth range of less than 30 m, and is a major
layer for irrigation extraction in the local region. The deeper aquifer occurs at a depth range of 4552 m, and consists of ne sand. Low permeability silty clay of 11 m thickness exists above the shallow aquifer,
which has a water table depth of 23m. The investigated Zhoukou landll with a thickness of 9.3m is embedded in this silty clay, which is likely
to be an aquitard. The thickness of low permeable silty clay underlying
the landll is approximately 1.7 m. Another silt and silty clay layer 20 m
thick occurs between the shallow and deeper aquifers. The aquifers are
widely distributed across the study area, and their thickness becomes
slightly thinner towards the south where the sediments become more
clay rich. In order to make comparison with groundwater hydrochemistry at different depths, apart from the two shallow aquifers,
one deep well (ZK1, Fig. 1) reaching 300m in depth was also investigated for hydrochemical analysis. The depth to groundwater in this well is
about 42 m below the ground surface, probably due to drawdown
caused by pumping in the deep layers.
The water table monitoring data shows that groundwater levels in
the study area varied from 2.3 m to 8.2 m depth. The hydraulic gradient
of the shallow groundwater is approximately 0.0014 and locally near
the landll, higher than this. The local water table gradients below
and around the landll are likely to differ from the regional gradient,
as landlls usually have different hydraulic properties compared to
the surrounding area. A local water table mound has been observed at
the Zhoukou Landll (water levels are higher than the surrounding
areas). This could be due to higher inltration capacity and preferential
recharge at the site, or pumping of groundwater in the areas outside the
landll. Groundwater levels in May 2009 were generally lower than
in December 2009 (after the wet season). According to the monitoring
data, the amplitude of the seasonal variation between wet and dry
periods ranges from 0.1 to 0.6 m.
Recharge to the alluvial aquifers consists of inltration from precipitation, rivers and channels, and leakage from irrigation return ows
near the landll. Groundwater discharges to small streams, wetlands,
and the Jialu River, and is subject to evapotranspiration. Groundwater
sinks include discharge via evapotranspiration into the shallow soil
zone, articial extraction, and out-ux of groundwater to surface water
in downstream areas. With the exception of ood periods (where surface
waters recharge the groundwater), groundwater discharges to the Jialu
River at all times. As Zhoukou city is located in the south of the Yellow
River alluvial fan, the saturated zone sediments are coarse-grained,
which creates a potential pathway for rapid transport of contamination.
These coarse-grained sediments are common throughout the Huaihe
River Basin and are typically associated with groundwater pollution
(Qu, 2010).

Fig. 3. Stable isotopic composition of water samples in the study area (relative to VSMOW).
The local meteoric water line (LMWL) represents the monthly averaged isotopic composition
of long-term precipitation at the monitoring station Zhengzhou, being part of the Global
Network of Isotopes in Precipitation (GNIP).

29

3.2. Stable isotope compositions

The 18O and 2H stable isotope composition of groundwater can
be analyzed in order to understand the recharge origins and circulation of the groundwater, and evaluate any possible evaporation
(Table 2). Stable isotopic compositions of groundwater range from
7.5 to 2.7 for 18O and from 71 to 34 for 2H. The mean
2H and 18O values are 56 and 6.1 for groundwater and 56
and 6.2 for surface water, respectively.
A plot of 2H vs. 18O for surface and groundwater is shown in Fig. 3.
The global meteoric water line (GMWL) corresponds to Craig (1961)
and the local meteoric water line (LMWL, 2H = 7.3 18O + 2.1, n = 11
from Jan. to Dec., r2 = 0.94) is based on 18O and 2H values of the average monthly rainfall monitored between 1985 1992 at Zhengzhou station (3443.2N, 11339.0E) some 200 km NW of Zhoukou city. The
rainfall data were taken from the IAEA network (http://isohis.iaea.
org). Most water samples are distributed along an evaporation line
(Fig. 3), which is approximately parallel with the GMWL and LMWL. A
wide variation in groundwater values from the study area on the right
side of the GMWL was observed. It is noted that this oxygen shift
could be caused by elevation effects and/or evaporative processes to
various extents prior to water reaching the saturated zone. The distributions of 2H and 18O in surface and groundwater samples are similar,
and near the LMWL, indicating that surface and groundwater have similar
origins (rainfall). Deep groundwater (from ZK; well depth of 300 m) has
lower values of 2H and 18O, indicating a colder climate during
recharge. This is common in the deep aquifers of northern China, where
much of the groundwater was recharged during the late Pleistocene
(Currell et al., 2012).
3.3. Inorganic macrocomponents in surface and groundwater
3.3.1. Physico-chemical characteristics of water samples
The temperature of all water samples ranged from 7.6 to 22.7C. The
groundwater was characterized by the pH values from 6.61 to 8.94.
Groundwater was characterized by low turbidity (0.11.9, mean value
of 0.7) in the winter season and high turbidity (0.917.2, mean value
of 5.9) in the summer season. Sewage water and leachate samples recorded a much higher turbidity of 79.290.1 with a mean value of 84,
suggesting that they may have more inuence on local groundwater
during the summer season. To some extent, turbidity can reect the
degree of contamination or leachate inuence in different water bodies.
A wide range of electrical conductivity values (396approximately
4000 S/cm) indicate presence of either contamination by leachate
(expected to have high salinity), and/or evaporation of groundwater
prior to/during recharge. CODMn, (expressed in oxygen mg/L), can be
regarded as an aggregative indicator reecting the extent of
groundwater pollution by organic and reducing inorganic matter
(MEP, 2002). The presence of relatively high CODMn (range of 0.08
46.7 mg/L, leachate = 40.3 mg/L) in the collected groundwater samples
near the landll indicates the threat of severe contamination of
groundwater.
Surface waters are generally Na-HCO3 SO4 or Ca-HCO3 Cl type
(according to the classication of Stuyfzand, 1986) with a TDS concentration ranging from 0.64 to 0.96 g/L with a mean value of 0.81 g/L.
Groundwater samples collected in December 2008 and December
2009 were found to be Ca Mg-HCO3 (Cl) type, and in May 2009 and
June 2010 were found to be slightly more Na and Cl-rich. TDS concentrations of groundwater ranged from 0.46 to 2.85 g/L, with a mean value of
1.11 g/L. Landll leachate (ZE) is Na Ca Mg-HCO3 Cl SO4 type with
1.62 g/L TDS, and sewage water (ZC and ZD) is Na-HCO3 Cl or
Na Mg Ca-HCO3 type with less than 1 g/L TDS. Hardness values
ranged from 142 to 2045 mg/L as CaCO3. Piper plots show that the
water type is closer to HCO3-type, and hence more benecial for
usage, in the winter season compared to summer (Fig. 4). Groundwater
salinity in the summer season (mean TDS concentration of 1.29 g/L)

30

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

Fig. 4. Piper diagram showing the hydrochemical composition of water samples around the Zhoukou landll aquifers. Groundwater samples show hydrochemical compositions close to
that of the surface water in the wet season.

was higher than in the winter season (mean of 0.97 g/L), indicating
greater amounts of leachate generated in the Zhoukou landll in
summer, which could be attributed to the rising water table and

subsequent mixing of leachate with groundwater water nearby. Some

evaporative effects in summer may also be responsible for the higher
TDS contents.

2
Fig. 5. Variations of some chemical parameters with distances away from the Zhoukou landll center. (a) NO
3 and Hardness; (b) TDS, F , Cl and SO4 ; (c) CODMn and As; (d) Fe, Mn,
Ca and Mg. TDS, Hardness, Cl, CODMn, As, Fe, Mn, Ca and Mg have obvious decreasing trends with the increase in distance from the landll center.

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

31

2
+
Fig. 6. Concentration contours for the Cl(a, a), NO
3 (b, b), SO4 (c, c), Mn (d, d), F (e, e), and NH4 (f, f) of groundwater samples from the shallow aquifer (b30 m depth), collected in
May 2009 and Dec.2009, respectively. Units are in mg/L.

Additionally, TDS, hardness and CODMn of groundwater showed an

obvious decreasing trend with increasing distance from the landll center (Fig. 5a,b,c), and TDS showed a decreasing trend with increasing
sampling depth (Fig. 5.d). These indicate that the landll contributes
salinity, hardness and CODMn to the adjacent groundwater. The concentration contours of several selected ions and elements in shallow
groundwater are shown in Fig. 6. It can be seen from these maps that
the concentration of Cl, NH4 and Mn (common characteristics of leachate)
decline away from the landll.

3.3.2. Major anions

A wide range of major ion compositions were observed, as shown in

the Piper plots (Fig. 4). HCO

3 and Cl accounted for 18.878.5% (mean
value of 55.6%) and 11.871.9% (mean value of 26.3%), respectively, of
total anions; similar to surface water (46.3% and 28.6%, respectively).
Three groundwater samples collected from the well ZKN (Table 1),
exceeded the proposed drinking water quality standards for chloride.
There is a denite attenuation of chloride in groundwater down gradient of the landll (Fig. 6a and a).

32

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

Fluoride (F) concentrations in groundwater range from 0.02 to

4.19 mg/L (mean value of 0.93 mg/L) and are from 0.46 to 2.66 mg/L
(mean value of 1.3 mg/L) in the surface water samples. The F concentrations in 33% of groundwater samples exceeded the drinking standard
of 1 mg/L. Among the groundwater samples collected in December
2008, only well ZB exceeded the maximum acceptable level, and there
were no wells that exceeded this standard in December 2009. However,
the majority (83%) of groundwater samples collected in May 2009 were
characterized by F concentrations greater than 1 mg/L, indicating that
F may be more susceptible to migrate in the aquifer during the summer. In addition, ne-grained sediments and the relatively stagnant
groundwater ow in this region are more likely to result in the uorine
enrichment (Gong et al., 2010). Long-term ingestion of high-uoride
groundwater is the major reason for endemic uorosis in this area
(Gong et al., 2010), a condition that affects human health by causing
damage to bones and joints (e.g. dental and skeletal ourosis) (Cauley
and Murphy, 1995). The existence of this long-term condition in the
region indicates that uoride had a geochemical source present in the
aquifer before the installation of Zhoukou landll. Groundwater uoride
concentration showed a strong correlation with sulfate (SO2
4 ) concentration (Table 3), and relatively lower F concentrations (0.49
0.86 mg/L) were detected in the sewage water and the leachate (e.g. ZC,
ZD, ZE). Although there is a big variation of F concentrations in May and
December 2009, it also can be seen from the hydrochemical isolines
map (Fig. 6e,e) that F shows lower concentrations surrounding the
landll. In this study, high F groundwater (N1 mg/L) was observed in
groundwater with high pH values (N 7.5); consistent with the ndings
of Cai (1999), Gong et al. (2010) and Currell et al. (2011). Therefore, if
the landll leachate is a signicant source of alkalinity, this could indirectly lead to greater levels of mobilization of uoride from natural geological
sources (e.g. Kim et al., 2012). Common F-bearing minerals (e.g., uorite,
hornblende) were detected in Funiu Mountain area (Gong et al., 2010),
which is located in the southwest of Zhoukou city and about 200 km
away from Zhoukou. Many hydrogeochemical investigations show F concentrations of groundwater in Xuchang and Pingdingshan area, which
close to the study area, range from 1 to 2 mg/L. However, the F contents
of groundwater are locally higher than 2 mg/L (even up to 4.19 mg/L at
the well DW09) in this study area. Apart from the geological background
source, phosphatic fertilizers may be responsible for high concentrations
of uorite in groundwater (Li et al., 2009; Shui and Zhang, 2009).
The majority of groundwater samples in this study were collected
from the shallow aquifer (less than 30m depth), and nitrate (NO
3 ) concentrations ranged from 0.1 to 487 mg/L (mean value of 59 mg/L) with
43% of these samples exceeding the Chinese standard of 20 mg/L NO
3 .
Surface water NO
3 concentrations ranged from 0.1 to 42.9 mg/L

(mean value of 13.7 mg/L) and nitrate could not be detected in the
sewage water nor the leachate (e.g. ZC, ZD, ZE). This indicates that
local agricultural activities (e.g. the use of N-fertilizers with precipitation inltration or irrigation return ow) are the primary cause of the
extensive groundwater nitrate contamination (Zuo et al., 2007), as opposed to any point source nitrate contamination from the landll site.

There is no signicant negative correlation between NO

3 and HCO3 , indicating little or no heterotrophic denitrication, which would otherwise continuously remove nitrate from the aquifer (Mohamed et al.,
2003). This is likely due to a lack of denitrifying bacteria, which use
the oxygen from nitrate to generate energy from organic carbon, releasing
bicarbonate and nitrogen gas to the system as byproducts (Babiker et al.,
2004). In the present study, groundwater collected from wells used for

agricultural irrigation and domestic use, has relatively high NO

3 and F
concentrations.
Biochemical reactions can produce ammonium (NH+
4 ) in groundwater, indicating organic pollution providing electron donors (Chapman,
1992). Nitrate reduction potentially occurs at the mixing zone of landll
leachate and shallow nitrate containing groundwater, with the presence
of ammonium and elevated nitrite at Z40, ZKW and Z16, indicating the
partial nitrication of the ammonium plume due to inltrating oxic
water. Nitrate reduction can cause disappearance of nitrate with depth
(Postma et al., 1991), also potentially affecting the shallow monitoring
wells (e.g., ZG10, ZG11) in this study. Groundwater with high nitrate
concentration (even up to 487 mg/L at DW09) was distributed in the
downstream area of the landll, and groundwater with low nitrate
concentration (b 0.2 mg/L) was distributed near the landll (e.g., ZG10,
ZG11, ZKE, ZKN), indicating that denitrication is likely a dominant
redox process at the downstream fringes of the plume. The contribution
of aerobic and nitrate-reducing environments to natural attenuation of
the major contaminants increases with the O2 and NO
3 concentrations
in ambient groundwater, and the extent of mixing with the leachate, respectively (van Breukelen, 2003).
Based on the theory of Gibbs free energy, the oxidation sequence for
the major chemical components at neutral pH can be in the order: O2,
2
and CO2 (van Breukelen, 2003; Wilson
NO
3 , MnO2, Fe(OH)3, SO4
et al., 2004). Most groundwater is characterized by dissolved oxygen
(DO) of more than 1 mg/L, indicating there is the aerobic aquifer environment, and so aerobic oxidation of organic matter is probably still a
major process. In terms of changes in solute concentrations along the
2+
are
groundwater owpath (Fig. 6), Cl, TDS, Fe, Mn, NH+
4 , and Ca
high near the landll site, decreasing as groundwater moves away from
the landll.
Additionally, while groundwater Cl concentrations show an obvious decreasing trend with increasing distance from the landll center

Table 3
Pearson correlation matrix for major ions and pH, EC and TDS of the groundwater around Zhoukou landll.

EC
pH
Ca2+
Mg2+
Na+
K+
CODMn
Cl
SO2
4
HCO
3
NO
3

F
Hardness
TDS

EC

pH

Ca2+

Mg2+

1
0.60
0.48
0.63
0.56
0.37
0.36
0.65

1
0.58
0.57
0.27
0.45
0.20
0.42

1
0.55
0.11
0.19
0.16
0.39

1
0.14
0.54
0.12
0.74

0.24
0.62

0.15
0.58

0.17
0.66

0.11
0.48

0.23
0.10
0.78
0.81

0.00
0.37
0.72
0.55

0.18
0.45
0.60
0.30

0.06
0.08
0.61
0.52

Correlation is signicant at the 0.01 level.

Correlation is signicant at the 0.05 level.

Na+

1
0.10
0.82
0.46
0.26
0.26
0.09
0.16
0.60
0.87

K+

1
0.01
0.51
0.17
0.33
0.10
0.21
0.42
0.32

CODMn

1
0.06
0.08
0.04
0.14
0.11
0.56
0.68

Cl

1
0.01
0.60
0.09
0.01
0.55
0.68

SO2
4

HCO
3

NO
3

Hardness

TDS

1
0.09
0.54
0.71
0.03
0.24

1
0.12
0.09
0.54
0.46

1
0.40
0.01
0.05

1
0.33
0.05

1
0.87

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

33

Fig. 7. Characteristics of some chemical parameters with well depth around the Zhoukou landll. (a) Ca and Mg; (b) SO2
4 , Cl and NO3 ; (c) Zn, Pb and As; (d) Fe, Mn and TDS.

(Fig. 5b and Fig. 6a, a), groundwater NO

3 , SO4 and F concentrations
2
do not follow this trend (Fig. 6), indicating that pollution of NO
3 , SO4
and F may be due to local anthropogenic activities (e.g., fertilizer utilization, discharging domestic waste water into aquifer locally) and geo2
and Cl
logical background, rather than landll leachate. NO
3 , SO4
concentrations in groundwater are characterized by a decreasing
trend with increasing sample depth, similar with other ions (Fig. 7); indicating that the combined solute load is high near the surface due to
the combination of anthropogenic inuences (agriculture and landll
leachate). The highest concentrations were found at depths of less
than 30 m, where the shallow aquifer is composed predominantly of
ne sand.

(0.02 mg/L) concentrations (Fig. 8b) were found in the groundwater

with the highest pH (8.5 and 8.9, respectively). However, it would appear that pH is not the only factor controlling the distribution of Fe

3.3.3. Major cations

Na and Ca are the most abundant cations in the groundwater with
concentrations of 30.2872.0 mg/L (mean value of 175.6 mg/L) and
13.7212.6 mg/L (mean value of 69.9 mg/L), respectively (Table 1;
Fig. 4). Ca and Mg in groundwater are characterized by an obvious
decreasing trend with increasing distance from the landll center
(Fig. 5d). Additionally, the highest concentrations of Ca and Mg
were found within the shallow aquifer (Fig. 7a). This indicates that
higher concentrations of these cations may be caused by leakage of
landll leachate into the groundwater. The high Mg concentrations
around the landll may result due to industrial waste like cosmetics,
cement and textiles are being dumped into the landll (McBean et al.,
1995).
3.3.4. Fe and Mn
High contents of dissolved Fe and Mn can be produced by reducing
conditions generated in the landll. Fe and Mn variations in water are
mainly controlled by oxidationreduction conditions and acidalkali
balance (Virkutyte and Sillanp, 2006). Fe and Mn can be oxidized by
anaerobic bacteria and under low pH conditions, concentrations will increase (Pitt et al., 1999). In this study the lowest Fe (0.05 mg/L) and Mn

Fig. 8. Scatter plots of CaMg (a) and FeMn (b) concentrations versus pH of groundwater
samples.

34

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

Fig. 10. Scatter plots of Fe versus As contents, showing that the highest concentrations of
As were observed in Fe-rich environments.

Fig. 9. Scatter plots of FeMn (a) and AsPb (b) concentrations versus SO2
4 concentrations of
groundwater samples.

and Mn, as an extremely high concentration of Fe (4.8 mg/L) was found

in well Z16, where the pH was slightly alkaline (7.7). The Mn concentration in 76% of all groundwater samples exceeded the National Chinese
drinking water standard of 0.1 mg/L. Fe and Mn have a negative correlation with SO2
4 concentrations in all groundwater samples (Fig. 9a)
which is not in agreement with Olas et al. (2004), who determined
that Mn has a strong correlation with sulfates resulting due to sulde
oxidation. The Fe and Mn concentrations also showed an obvious decreasing trend with increasing distance from the landll center
(Fig. 5d and Fig. 6) and with increasing sample depth (Fig. 7d), indicating higher concentrations of Fe and Mn caused by inltration of reducing leachate. In contact with the process of reducing leachate from the
landll, manganese and iron oxyhydroxide minerals in the subsoil will
be more soluble in a reducing environment than in the natural oxidizing
environment (Deutsch, 1997). The low Eh conditions (b 50 mV detected in observation wells ZKE and ZKS in December 2009) can enhance the dissolution of both the manganese and iron oxide and
hydroxide minerals beneath and downgradient of the landll. Variations of groundwater level in different seasons may change the redox
environment in the aquifer. Away from the landll, the reconstruction
of oxidizing conditions should effectively lower the dissolved concentrations of Fe and Mn owing to the low solubility of their minerals
under oxidizing, near-neutral pH conditions. Elevated levels of major
cations present in groundwater may partially result from cation exchange reactions driven by the high levels of Fe, Mn, NH+
4 near the
landll (Deutsch, 1997). Cation exchange with clays may be an
important process responsible for the high concentrations of NH+
4 ,
Fe, and Mn at landlls. As the concentrations of Fe, Mn, and NH+
4
decrease away from the landll, the typical major cations will be
preferred on the exchange sites. Additionally, there will be the effects
on absorbed concentrations due to the low pH and Eh beneath the
landll.

3.3.5. As, Se and Hg

During the sampling campaigns, ZKS had high concentrations
(0.0240.052 mg/L) of As, which were signicantly higher than the
maximum allowable concentration (0.01mg/L) according to the National
Chinese guidelines. ZG10, Z16 and ZKE recorded As concentrations of
14.9, 11.0 and 14.0 mg/L, respectively. If these values are excluded from
the dataset, the mean concentration of As in the remaining water samples
was 0.003 mg/L, which is below the maximum allowable concentration.
Consistent with the ndings of Varsnyi et al. (1991), the Fe concentration
in the groundwater strongly inuenced the distribution of As with the
highest concentrations of As (up to 0.052 mg/L) observed in Fe-rich
(Fig. 10) and SO2
4 -poor environments (Fig. 9b). Additionally, groundwater As concentrations were characterized by an obvious decreasing trend
with increasing distance from the landll center (Fig. 5c) and increasing
sample depth (Fig. 7c). In general, Se and Hg were found in very low concentrations (up to 7.2 g/L and 0.2 g/L, respectively) without exceedance
of the NC standards.
3.3.6. Heavy metals of surface and groundwater
Generally, landll leachates contain only modest concentrations of
heavy metals as the metals are subject to strong attenuation by sorption
and precipitation (Christensen et al., 2001). The zinc (Zn) concentration
ranged from below the detected limit (BDL) to 0.065mg/L, with the majority of samples recording a low concentration that did not exceed the
World Health Organization (WHO) and National Chinese (NC) standards. The presence of zinc in the groundwater indicates that the landll
may be receiving waste batteries and uorescent light bulbs and is a
cause for concern with regards to plant and aquatic life (Al-Yaqout
and Hamoda, 2003). Aluminum (Al) levels ranged from b0.02 to
1.1 mg/L with 21% of groundwater samples exceeding the WHO and
NC standards (0.2 mg/L). It can be seen from Fig. 9b that low sulfate corresponds to high Pb. In general, heavy metals of groundwater samples
are characterized by high concentrations in the monitoring wells as is
seen in the samples taken in December 2009 (Fig. 11). Lead (Pb) concentrations in the groundwater ranged from BDL (b0.002) to
0.038 mg/L. Pb concentrations of N 0.01 mg/L were also found in some
wells. Possible sources of lead contamination may be batteries,
photographs, old lead-based paints and lead pipes disposed at the landll, which are toxic to all forms of life at this level (Al-Yaqout and
Hamoda, 2003). Acidity in leachate causes lead to be released from refuse, for example, the highest Pb concentration of 0.038 mg/L occurred
with a pH value of 6.6 and was observed in well ZKN in December
2009. Zn and Pb concentrations of groundwater samples were also characterized by an obvious decreasing trend with increasing sample depth
(Fig. 7c). The highest concentrations of Pb were observed in the SO2
4 poor environments (Fig. 9b). Cd and Cr concentrations ranged from
BDL (b0.001)0.008 mg/L and BDL (b 0.004)0.02 mg/L, respectively,
with the lower concentrations not exceeding the WHO and NC

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

35

Fig. 11. Variation of contaminant concentrations in the selected monitoring wells during three sampling campaigns.

standards. The high concentrations, however, indicate that there

will be some concerning human health risks caused by high intake of Cd (Ikem et al., 2002) and Cr (VI) (Wedeen and Qian,
1991). Seasonal variations of the major heavy metals in groundwater (Fig. 11) showed that these contaminants are characterized by higher concentrations in May 2009 and lower

concentrations in December 2008 and December 2009. Generally, heavy metals do not seem to constitute a signicant pollution
problem at the landll site, partly because concentrations in the
sewage water and the leachate are often low, and partly because
of strong attenuation by sorption and precipitation in the sedimentary aquifers (Xie, 2011).

Fig. 12. Results of the principal component analysis (PCA) for major chemical components in groundwater samples surrounding the Zhoukou landll site, showing the plots of variables
and loadings (a) and (a)Principal component loading plot for the water samples collected in May 2009 and Dec.2009, respectively; (b) and (b)component score plot for the water
samples collected in May 2009 and Dec.2009, respectively.

36

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

3.4. Principal component analysis

3.5. Contaminant transport model

To better distinguish the hydrogeochemical processes controlling

the groundwater hydrochemical composition, principal component
analysis (PCA) (a common multivariate statistical method) was applied
to the groundwater samples. The total number of components from PCA
can indicate potential sources of groundwater salinization and provide
insight into the interpretation of the data. In this study, the multi
2

variables include Ca2+, Mg2+, Na+, K+, Fe, Mn, NH+

4 , SO4 , NO3 , Cl ,

F , HCO3 , and TDS in groundwater samples (the dataset shown in

Table 1). Al, Pb, SiO2 and As variables were not included because they
are frequently below the quantication limit, and all analytical values
less than dbl are replaced with zeros. The water samples collected
from the shallow aquifer (1325 m depth) in different time periods
(May 2009 and Dec. 2009) have been analyzed separately. The calculation was carried out with SPSS 16.
After autoscaling, two signicant components were identied to
represent 68.3% of total sample variance (43.3% for PC1 and 25.0% for
PC2) in May 2009 (Fig. 12a,b), and 73.7% of total samples variance
(46.5% for PC1 and 27.2% for PC2) in December 2009 (Fig. 12 a,b), respectively. The third component takes into account only 13.4% and
9.1% of the total variance, respectively, and was not considered in the
present analysis. Fig. 12 shows the loading plot and substantiates that
the rst component is mainly related to Na, Ca, Mg, K, Cl and TDS in
the two sampling periods, whereas the second component is mainly
related to F, NO3, SO4, and HCO3 in May.2009, and to Fe, Mn, and NH4
in Dec. 2009.
In this context, three groups of samples can be identied, seen in
Fig. 12a, a. In space variables, the PC1 factor takes high positive loading
for the most chemical components in groundwater except for NO3, SO4,
Fe, NH4 and F that show a negative loading. Group 1 can be described by
mineralization of groundwater by water-rock interaction. The negative
loading for Group 2 and Group 3 that corresponds to high positive
loading for Group 1 may provide insight into the anthropogenic
pollution, including leakage of landll and fertilizer input through irrigation inltration along the groundwater ow paths surrounding the
landll.
The axis PC2 opposes Fe, Mn and NH4 to NO3, SO4 and HCO3. However, there are different loadings with opposite trend on these chemical
components in different sampling periods, due to the groundwater
level uctuation and redox environment variations. The opposite evolu2+
in PC2 in May 2009 indicates that
tion of Alkalinity (HCO
3 ) and Ca
the increase of Ca2+ content in groundwater is likely related to gypsum
dissolution and/or cation exchange and not carbonate weathering.
There is also a notable decline in sulfate (Fig. 6c,c) near the landll
due to sulfate reduction. Compared with the ambient groundwater,
the sulfate concentration in the landll leachate has generally lower
values, and may not maintain a degradation potential equal to iron reduction. The elevated concentrations of dissolved Fe and Mn in groundwater near the landll indicate these elements mainly mobilize under
reducing conditions from landll leachate.
Based on the analysis of variable loadings on PC12 in Fig. 12a, a, the
different factors controlling on groundwater hydrochemical components can be proposed (see Fig. 12b, b). The values of factor scores
are lower or higher than 0 depending on their relationship to the intensity of chemical processes that each factor represents (Szynkiewicz
et al., 2011). In summer season, the irrigation return ow and waterrock interaction make large contributions to groundwater quality towards the downgradient area (e.g., DW18, DW25, DW23, Z34), and
the leachate pollution plays the dominant role in controlling groundwater quality surrounding the landll site (e.g., ZKS, ZKE, ZKW). Among
these water samples, DW18 with high score N+4 in PC2 is strongly associated with nitrate pollution from agricultural practices. In the winter
season, the leachate pollution and the water-rock interaction give high
scores in PC2, having great inuence on groundwater quality around the
landll site.

In order to investigate the extent of migration of the landll leachate

into the sand aquifer and the role of the clay/silt layers, a chloride transport model along a cross section was constructed. Although groundwater
ow in the aquifer is essentially horizontal from the area north of the
landll to the area south of the landll (Fig. 1), the zone of leachate contamination beneath the landll has penetrated downward through the
entire upper sand aquifer thickness to a depth of 1325 m (Han et al.,
2013). This indicates that the vertical ow is also a primary inuence on
the distribution of contamination zone. The contaminant transport
model was used to assess how landll leachate may migrate into the
upper sand unit, or whether the deeper sand unit could be contaminated.
Chloride ion was selected as the conservative tracer because it
is generally not subject to undergo any physico-chemical reactions
(e.g., adsorption, precipitation, and biological degradation) in the aquifers
(Christensen, 1992), and usually it is characterized by high concentrations
in leachate and leachate-contaminated groundwater near the landll.
Therefore, chloride can be used to study dispersion and dilution of a contaminant plume. Other conservative solutes are expected to behave in a
similar fashion and could be simulated, given data on inuent and background concentrations. The investigation of organic contamination in
shallow groundwater surrounding Zhoukou landll showed that there
is no inow of polluted groundwater into the river and sewage ditch,
and the contaminated river and waste water from sewage ditch does
not generally recharge the groundwater body (Han et al., 2013).
The landll body is the main pollution source for groundwater contamination in the study area. No other point sources or distributed
sources of chloride ion were simulated in this study. The computer
code MODFLOW-2005 (Harbaugh, 2005) was used to simulate the
groundwater ow, and the computer code MT3DMS (Zheng, 1999),
was used to simulate the two-dimensional advective-dispersive transport of a conservative solute down gradient from the landll site. The
2D advection dispersion equation is written as (Zheng, 1999):
C
2 C
2 C
C
C
Dx 2 Dz 2 vx
vz
;
t
x
z
x
z
where C is dissolved concentration; t is time; Dx, Dz are dispersion
coefcient; vx, vz are velocity component in X and Z direction. The
3.5.1. Model geometry and parameters
Based on the analysis of groundwater hydrochemistry and hydraulic
dynamics in the study area, a reliable hydrogeological conceptual model
was established, shown in Fig. 13. The N-S cross section was chosen to
construct the contaminant vertical transport model (Fig. 13a). Each of
the silt/clay and sand units shown in Fig. 13a was discretized into 2 to
4 model layers. The cross section was vertically discretized 19 layers
in total, with a uniform horizontal 20 m grid cell size with thickness of
23 m (Fig. 13b). The top boundary of the cross section model receives
recharge from precipitation. The bottom boundary of the model is restricted by the depth of available investigation boreholes in this site
and is assumed no ow. Groundwater recharge in the study was estimated of ~36 mm/yr (Qu, 2010), and the rate of leachate entry to the
aquifer was estimated of 60280 mm/yr (Song et al., 2012). The ux
owing in/out in the lateral boundaries of the sand aquifer were estimated according the geometry of the boundary and the regional
hydraulic gradient.
A representative value of the horizontal hydraulic gradients in the
regional aquifer covering the landll site is in the range of 0.0002 0.00033 (Qu, 2010). Based on the measured water level contours in December 2009, the hydraulic gradient near the landll is approximately
0.0014. The values for hydraulic conductivity from 12 pumping tests
in the ne- and medium grained sand are in the range of 1112 m/d
(Qu, 2010). The effective porosity value ranging 515% is anticipated
for the aquifer made up of ne sand in this site. Based on the data on

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

37

Fig. 13. (a) Model geometry for the transport model and (b) nite difference grid and boundaries for the ow model.

hydraulic gradient (i), effective porosity (n) and hydraulic conductivity

(K), values of the average groundwater seepage velocity (v) were obtained as v = Ki/n, in a range of 41112 m/yr.
No information is available about the hydraulic conductivity of
the silty clay and silt units at this site. The hydraulic conductivity values
of the clay/silt layers are therefore estimated through sensitivity analysis by calculating water level distribution and travel time of leachate.
Mechanical dispersion caused by velocity changes related to
heterogeneity is generally negligible in porous media with a very low
hydraulic conductivity such as silt and clay. For the purpose of modeling
vertical migration of contaminants in the silt/clay layers, mechanical
dispersion is neglected and only advection and diffusion were
considered.

3.5.2. Model results and sensitivity analysis

Sensitivity analysis is conducted by running the model by varying
parameters of vertical hydraulic conductivity of the clay/silt layers and
effective porosity. The values of vertical hydraulic conductivity of the
clay/silt layers were assumed to be in range of 0.00010.01 m/d. Given
the operation time of the landll since 1998, the travel time through
the pathlines starting the bottom of the landll to the top of upper aquifer serves as a useful response for model sensitivity analysis. The travel
time is calculated by the particle tracking software MODPATH (Pollock,
1994) and is a sensitive to the hydraulic conductivity and effective porosity. The effects of uncertainty in vertical hydraulic conductivity and
effective porosity are shown in Table 4. The sensitivity shows that variation of vertical hydraulic conductivity in three orders of magnitude results in about one order of magnitude change in the travel time.

Reducing the effective porosity to 1/3 of base value (0.15) also decreased the travel time to about 1/3 of the base value.
The model is run 13 years to represent the operation time of the landll since 1998 to 2010. Several model runs are made with longitudinal
dispersivity (L) as 1, 10 and 100 m. Vertical transverse dispersivity is
assumed 1% of the longitudinal dispersivity. The simulated chloride
concentration show signicant different break-throughs in the upper
aquifer beneath the right lower corner of the landll (Fig. 14). Longitudinal dispersivity of 1m resulted in a maximum value of chloride concentration of ~500 mg/L at the end of simulation, which is much lower than
chloride concentration observation. Although longitudinal dispersivity
of 10 m and 100 m can produce chloride concentration of ~1000 g/L at
the end of 2010, the shape of the break-through is signicantly different.
For 100 m of dispersivity, the concentration reached about 760 mg/L
only after 2years of simulation, which may not be anticipated considering
the operation history of the landll. The simulated values considered
reasonable for horizontal and vertical transverse dispersivities in
the sand aquifers are 10 m (longitudinal) and 0.1 m (vertical),
respectively.

Table 4
Average travel time under different Kv and effective porosity along the pathlines beneath
the landll to the top of upper aquifer.
Kv (m/d)

0.0001

0.001

0.01

0.1

Travel time (yr)

Effective porosity
Travel time (yr)

110.7
0.05
7.3

23.4
0.1
14.7

22.0
0.15
22.0

13.4
Fig. 14. Concentration break-through in the upper aquifer beneath the right lower corner
of the landll for different dispersivities.

38

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

Fig. 15. Simulated chloride plume 13 years after the implementation of landll in 1998 based on (a) steady sate ow model and (b) transient ow model considering seasonal variations in
groundwater level.

At the end of 13years, the estimated movement of the leachate front

(concentration contour line of 10 mg/L) would be ~60 m to south assuming a steady state ow. These estimates indicate the lateral migration of the plume in the aquifer is limited. The simulated chloride
plume was constrained in the upper sand unit in the 13 year period
since the beginning of operation of the landll (Fig. 15a). Another factor
that may affect the migration of plume beneath the landll is the seasonal variation in water levels, which may result in variation in the vertical hydraulic gradient. The average annual recharge used in the steady
state ow model (scenario 1) for transport simulation (Fig. 15a) was
therefore redistributed into each season according to the ratio of seasonal precipitation and annual precipitation in each corresponding season. The transient ow model (scenario 2) was applied to simulate
contaminant migration in the aquifer (Fig. 15b) under these conditions.
The model results indicate that the transient vertical hydraulic gradient
may be the primary cause for the migration of contaminant beneath the
landll. Under the transient ow, the front of the chloride plume vertically reaches a deeper depth from the ground surface. The simulated
~0.35 meter difference between spring and summer water table caused
a higher magnitude of vertical gradient over summer and autumn, and
therefore resulted in several meters of vertical migration of the contaminant plume.
4. Conclusions and implicated measures
The large number of uncontrolled landll sites in China, such as the
site in Zhoukou is an increasing environmental and public health concern, and has been identied as a major threat to groundwater quality.
This study of the isotopic and hydrochemical composition of surface
and groundwater around the Zhoukou municipal landll has been conducted to better understand the extent of contamination from landll
leachate, for a case where unlined and un-regulated lling occurred,
accepting typical waste streams. Stable isotopes (18O and 2H) indicate
elevation effects and/or evaporative processes prior to water reaching
the saturated zone, and show that surface and groundwater have similar origins of recharge. Groundwater below and around the landll site
has been contaminated by leachate, clearly demonstrated in the presence of reducing conditions and high concentrations of TDS, Cl, NH+
4 ,
Fe and Mn close to the site, with obvious decreasing trends with increasing distance from the landll center, sample depth.
The analysis of NO
3 concentration distribution shows that agricultural activities (e.g., the use of N-fertilizers) have also extensively

inuenced groundwater quality in the study area. Under low pH and

Eh conditions, the concentrations of dissolved metals (such as Fe and
Mn) in the groundwater increases. The data show the highest concentrations of As were observed in Fe-rich environments, while F (probably
present as a natural geological source) is more elevated in waters with
high pH. Se, Zn, Cd, Cr and Hg are found in very low concentrations
without exceedance of the WHO and NC standards, while As, Al and
Pb locally exceed these standards. In general, heavy metals do not
seem to constitute a signicant pollution concern at the landll site,
partly because the heavy metal concentrations in the sewage water
and leachate are often lower than the WHO and NC standards, and partly because of strong attenuation by sorption and precipitation in the
sedimentary aquifers. TDS, Cl, NH+
4 , Fe and Mn concentrations in
groundwater can be identied as the main indicators and make contribution to the groundwater pollution caused by landll leachate
percolation.
A two-dimensional advectivedispersive transport model was established by using MODFLOW and MT3DMS to simulate the chloride
plume in the upper sand unit. Two scenarios (steady state and transient
ow model) were simulated and discussed. Chloride transport simulation
shows that after 13 years operation of the landll, the contamination
plume is still constrained in the upper aquifer. The seasonal dynamics of
the hydraulic condition, such as recharge and water level temporal variations should be investigated further to evaluate the migration of the
plume beneath the landll. Based on transient modeling, seasonal changes may be an important inuence on vertical hydraulic gradients and
therefore vertical ow of contaminants.
Generally, groundwater around the Zhoukou landll is not suitable
for drinking water, and some remedial measures should be considered
to improve the groundwater quality around the municipal landll, particularly given the high levels of domestic and agricultural groundwater
use in this region. The landll itself is non-engineered, without any bottom liner and leachate collection and treatment system. Therefore,
leachate can easily nd a path into the subsurface environment and continue to migrate in coming years. Some feasible options for improving
groundwater quality are as follows: (i) Cover the landll with an impermeable clay in order to prevent rainwater from inltrating the waste
site and reaching the landll base. (ii) Extract and recycle the leachate
from the landll base so that less leachate will enter the underlying
aquifer. (iii) Treat and purify the groundwater around the landll for agricultural irrigation and domestic use in order to eliminate the high NO
3
and F concentrations. (iv) Close the landll. (v) Increasing the

D. Han et al. / Journal of Geochemical Exploration 136 (2014) 2439

evapotranspiration rate by planting vegetation cover over the landll in

order to reduce leachate production.
Acknowledgments
This work has been carried out under the Exploratory Forefront Project (No. 2012QY007) for the Strategic Science Plan in the Institute of
Geographic Sciences and Natural Resources Research, Chinese Academy
of Sciences, and was nancially supported as part of a groundwater
survey project titled Investigation and evaluation of typical contaminated sites in Zhoukou region of Huaihe River Plain (no. 1212010634505).
The authors are thankful to M.S. Xie Shiyong and Qu Zewei from China
University of Geosciences for their assistance with eld work preparation
and analyzing water samples in laboratory. We also thank the anonymous
reviewers for their valuable comments and suggestions.
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