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Journal of Geochemical Exploration 136 (2014) 24–39

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Journal of Geochemical Exploration
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Evaluation of the impact of an uncontrolled landfill 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

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
Center for Water Research, College of Engineering, Peking University, Beijing 100871, China
School of Environmental Studies, China University of Geosciences, Wuhan 430074, China

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
Uncontrolled landfill
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 landfill aims to better understand the possible impact of leachate percolation on groundwater quality. The study examined groundwater inorganic contamination around a municipal landfill site in Zhoukou city, Henan province, China. Stable isotopic compositions (δ18O and
δ2H) and concentrations of various physico-chemical parameters were determined in surface and groundwater
samples collected from the study area. δ18O and δ2H 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 identified TDS, Cl−, NH+
4 , Fe and Mn
concentrations as the main indicators of groundwater pollution caused by landfill leachate percolation. The groundwater quality of shallow aquifer is likely dominated by irrigation return flow in the summer. A two-dimensional
advective–dispersive transport model was established using MODFLOW and MT3DMS to explore the controls on
contaminant transport. Chloride transport simulations with steady state and transient flow models show that the
contamination plume is still constrained in the upper aquifer after 13 years of operation of the landfill. 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 influence on the migration of the plume beneath the landfill by controlling vertical hydraulic gradients and fluxes. In
general, the shallow groundwater (within 30 m depth) around the Zhoukou landfill 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 landfill 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 landfill-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 landfill

⁎ Corresponding author.
E-mail address: (D. Han).
0375-6742/$ – see front matter © 2013 Elsevier B.V. All rights reserved.

leachates, generated by excess rainfall percolating through waste
dump, are significant 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
3 ) from uncontrolled landfills 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

/ Journal of Geochemical Exploration 136 (2014) 24–39 water (δ18O. in the confluence of the Ying and the Jialu Rivers.. 25 Zhoukou city is located in the southeast valley of the Huaihe River Basin. 1998. 2007). Osenbrück et al. Identification of the sources of contamination and understanding the pathways of contaminants to and Fig. 4—groundwater monitoring wells (sampling wells with labels in Table 1). Study area and location of sampling sites around the Zhoukou landfill. 1998). 6—shallow groundwater table contours (m a. Drinking ungraded water and contaminated groundwater long term can result in endemic diseases. 8—flow direction of surface water. Of the seven large rivers in China. Foster. 2010) and both urban industrial and domestic waste and sewage discharge to surface water and groundwater. δ2H). 1). . 5—Surface water sampling sites. which belong to tributaries of the Huaihe River (Fig.l) from the monitoring data in December 2009. increasing demand for water is conflicting with water resource shortages.. 3—waters.. have been used to provide an improved understanding of the complex hydraulic and hydrological conditions present in urban areas (Barrett et al.D. LEGEND: 1—residential area. Morris et al.s. 1. 2006. agricultural and domestic use in Zhoukou city (Zhao et al. Groundwater is the main source of water supply for industrial. Groundwater quality around Zhoukou city has been deteriorating rapidly over the last few decades. the Huaihe River has the highest population density and the most serious water contamination issues (Cui and Fu. 2—landfill. 1999. 7—major groundwater-flow direction.. With rapid economic development in many cities of the Huaihe River Basin. Han et al. severely restricting the sustainable utilization of the region's water and the development of many local economies.

Over 60% of total precipitation occurs in the wet season (July–September). These aquifers consist of inter-bedded fine sand and silty sand. Groundwater samples were collected from production wells at a range of depths (9–300 m). the waste layer composed of domestic waste is 9.3 × 106 m3 for the whole of Zhoukou city. 2011). Hydrogeological bore logs can be seen in Fig. 1. and relate this to the site's hydraulic properties (iv) assess groundwater quality and put forward some remedial measures for reducing further groundwater contamination. 48 sampling sites. 2010). between longitudes 114°34′ and 114°43′ E and latitudes 33°33′ and 33°43′ N (Fig. 1). the Jialu River to the west.3 m thick. with a hydraulic conductivity of 12–16 m/d (Qu. Typical hydrogeological bores of the Zhoukou landfill for monitoring water level. occupying a total area of 18 km2. which covers an area of 214 km2. Deep groundwater exploitation is mainly used for urban living and industrial utilization. The study area borders the Ludong Trunk Canal to the north.2‰ from southeast to northwest. including 41 groundwater and 7 surface water sites. the shallow aquifer is within 30 m below the ground surface. 2.1 m/d. Shallow groundwater extraction. Around the landfill. and 90 m from east to west and is currently surrounded by the city planning area. In 2005. The research results provide a scientific foundation for protecting and managing groundwater resources in Zhoukou and similar areas. This study focuses on investigating groundwater chemistry of the shallow aquifer within 13–25 m depth. A sewage ditch is located to the east of the landfill. tectonic and hydrogeological conditions of the Yangwu River alluvial fan. The elevation of the study area ranges from 45 to 51 m above mean sea level. December 2009 and June 2010. and we hope provides a good example for further groundwater contamination research in China in the coming years. Fig. Study area The study area is located in the north of Zhoukou city. Surface water samples were collected from a sampling depth of 0. showing the major geological layers in the vicinity of the landfill. The landfill has been accepting municipal solid waste from the City of Zhoukou since 1998 and was closed in 2010. and the Low-lying Gully to the east. The hydraulic parameters of the aquifers are referenced from the results of pumping tests (Tong. 2. At the center of the landfill (ZKC in Fig. 2). The accumulative amount of solid waste reached approximately 13 × 104 m3. The locations of the sampling stations are shown in Fig. respectively. Han et al.7 m and a hydraulic conductivity of 1. ZKC and ZKS′ are located at the center and some 150 m south of the landfill. the Ying River to the south.5m below the surface. 2012). with an average annual potential evapotranspiration (PET) (annual mean water surface evaporation) of 1736 mm and an annual precipitation of 728 mm (Xie. which is mainly used for irrigation and rural drinking water. Materials and methods 2. were chosen for analysis and samples were collected in December 2008. .2–18. 2. with a thickness of 5–23. fed by baseflow at most times of the year. The length of the landfill site measures 200 m from south to north. May 2009.1. in order to: (i) investigate the distribution of inorganic macrocomponents and minor elements (including heavy metals) in surface and groundwater around the Zhoukou landfill. One deeper aquifer exists at a depth of 45– 52 m.26 D. The Ying and the Jialu Rivers in the study area both belong to the Huaihe River Basin and are perennial rivers. (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. with a mean land surface slope of 0. the total yearly groundwater extraction had reached 1163. (iii) study the spatial characteristics of the area impacted by the landfill. accounts for about 90% of the total groundwater exploitation (Qu. where the long-term leaching of waste and sewage discharge has had a serious impact on ambient groundwater quality. / Journal of Geochemical Exploration 136 (2014) 24–39 within the aquifers are essential for accurate prediction of water quality and for appropriate management of the water resources in Zhoukou city. The climate in this region is a continental monsoonal type. 2010).2. Sampling and analysis Based on prior analysis of the geologic. 2. The present study undertook hydrogeological and hydrochemical– isotopic monitoring of the shallow aquifers underneath and around the Zhoukou uncontrolled landfill. Henan province.

6 8.0 274. 2009 Dec.0 346.33 0.1 17.1 0.9 158.0 149.5 321.0 13.0 172.5 0.9 11.1 b0.3 122 30.5 35.5 18.66 1.33 7.2–8.02 1.8 380.82 2.02 0.6 5.2 0.6 0.6 128 76.9 0.6 0.0 80. 2009 Dec.2 55 6.1 12.92 0. 2009 Dec.1 4.7–22.02 b0.01 680 0.07 0.02 0.6 7.2 0.71 7.4 24.96 7.1 61.01 0.2008 Dec.4 95.3 123 69 69.5 147.1 13.1 569.1 b0.3 17 17 16.9 0.01 0.2 122.43 0.2008 Dec.480 0.5 17.0 58.0 179.2 0.3 1.8 0.3 7.02 0.1 13.0 0.004 0.26 (continued on next page) .5 9.02 0.77 0.004 0.8 120.46 6.01 0.07 0.1 3.1 b0.8 126.3 0.09 7.04 0.2008 Dec.3 0.7 71.59 6.1 16.3 161. 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 13.68 13.05 0.01 0. 2010 Jun.52 0.97 8.4 4.2 0.2008 Dec.2 57.8 0.1 0.1 0.1 15.D.6 111.6 110 46.5–25.02 0.11 0.2–9.6 9.5 49.1 0. 2008 1.35 1. 2009 Dec.005 0.0 506.0 1.05 0.5 212.14 1.83 0.2 b0.6 39.39 7.02 b0.8 1.98 1.004 0.97 7.2 b0.02 0.01 0. 2008 2. 2009 Dec.0 111.8 20. 2010 Jun.5 0.6 9.47 0.4 0. 2009 Dec.01 0.4 16.9 0.5 101.6–25.6 9.2 0.6 1.8 1.7 0.1 b0.24 0.33 0.0 93.63 0.5 90.15 1.7 102.9 29.2 Dec. 2009 Jun.01 0.02 0. 2009 Dec.0 51.98 1.6–25.3 0.7 16.8 1.7 2.02 224 b0.1 May 2009 0. 2009 Dec.17 0.2008 Dec.39 1.8–22.7 51.2008 Dec.4 20.03 47.6 14.0 521.62 1.08 0.6 92.6 24.6 0.1 b0.0 35.0 202.2008 Dec.7 327.0 7.1 b0.1 1.2 314.1 58.1 b0.0 300.01 0.2–25.2–24.66 0.91 0.6 13.0 331.9 0.9 6.6 13.4 0.16 1.6 4.24 0.20 634 5.03 0.15 1.7 6.1 55.1 18.89 0.0 720.3 96.6–17.2 b0.07 0.7–24.9 14.6 19.5 32.19 1.5 16.7 33.7 b0.01 0.6 0.24 0.2 0.99 0.05 0.7 11.6 37.8 15.6 18.45 0.33 0.5 18.7 175.0 150.2 65.05 0.3 0.14 0.8 2 1.05 0.2 0.9 691.7–22.49 0.8 64.3 14.2 7.5 80.02 b0.1 b0.3 7.3 660.0 66.7 Hg As Se NH4+ H2SiO3 CODMn Cl− Cd Pb Zn Cr6+ (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) ID Sampling time ZA ZB ZC ZD ZE ZF ZG Z6 Z6A SW29 SW49 SW59 ZK1 ZKE ZKW ZKS ZKN ZF Dec.05 0.01 0.10 492 0.59 1676 1652 1353 3999 1164 1219 1378 1494 787 1502 1726 1985 1412 −91.9 11.55 80.02 829 0.56 0.4 1.6 0.02 0.2 b0.730 0.00 0.9 104.1 0.2008 Dec.2 0.8 10.0 115.6 174.53 0.0 52.76 13.35 0.42 7.6 65.02 0. 2008 1.4 Dec.3 18.41 0.1 1.27 7.4 0.0 656.0 138.7 39.6 104.1 0.2008 Dec.05 0.0 18.1 0.2–25.0–25. Han et al.97 40.1 41.2 b0.86 0.28 0.14 0.6 53.4 0.11 659 1.16 0.3 0.5 51.05 0.8 0. 2009 Dec.1 1.7 27.0 140.2009 May 2009 May 2009 May 2009 May 2009 May.0 277.93 7.2–26.28 0.8 0.05 0.05 0.06 5.3 12.4 27.6 25.1 12. 2009 Dec.0 151.7 Dec.7 59.63 7.2–25.0 137.94 7.0 2.2 0.9 0.9 0.02 230 b0.9 11.2 0.0 73.2008 Dec.0 69.2 0.13 0.005 0.3 11.4 68.6 55.6–25.1 Dec.92 0.29 3.4 May 2009 0.1 11.2008 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. 2008 0.0 631.3 1.2 b0.7 126.05 0.02 399 15.0 Dec.9 71.1 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. 2009 Dec.1 0.08 0.9 81.0 159.3 79.1 11.46 0.1 20.8 0.2 1.0 193.04 0.005 0.32 0.013 b0.5 3.1 0.7 7.8 4.6 Dec.45 0.8–23.0 73.8 4.11 2.46 0.8 74.8 294 0.0 Dec.7 4.2–25.082 0.47 964 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 6.1 1 1 b1.9 328.61 7.89 7.0 61.63 0.1 1.01 0.49 0.48 0.5–13.15 0.05 0.4 83.01 0.5 38.25 0.41 18.3 119.3 47.85 2.02 1188 110.3 73.13 2. 2008 b0.1 b0.0 Dec.8 56.42 0.54 2.4 220 369 196 169 255 184 198 234 872 580 158 202 185 202 174 179 182 175 161.1 30.13 0.01 1032 0.6–25.49 6.61 1809 1162 194 189 2.56 0.1 67.2–28.4 2.22 b0.15 0. 2009 Dec.8–9.3 0.05 0.25 141 0.11 0.4 20.3 18.2008 Dec.8 179 62 206 125 114 81.73 7.10 838 126 0.4 103.02 0.6 124.31 1.17 0.5 10.0 F− NO− 2 I− Hardness TDS (g/L) 2.3 75.8 93.02 7. 2009 Dec.3 8.2008 Dec.1 b0.2 50.5 34.3 17.09 321 b0.73 2.76 1.3 13.4 0.01 0.0 168.5 58.56 0.0 148.6 17.980 b0. 2008 4.7 1.01 0.8 16.01 0.5–8.2 0.31 0.0 599.0 189.0 7.8 45.4 3.98 17.3 0.54 4.7 68.03 3.5 22 7.3 0.2–24.01 0.05 0.1 12.0 SO2− 4 HCO− NO− 3 3 46.2 12.4 0.2–25.1 72.014 0.21 7.6 10.46 4.02 0.7 23.02 0.005 0.29 2.4 227.6 1.09 0.2 32.9 210 81.39 7.1 11.7–24. 2008 2.8 8.2 0.0 777.8 16.0–24.9 18.2 106.8 12.1 7.92 2.1 b0.19 7.5 0.7 0. 2008 4.0 53.05 0.7 102 85. 2010 Jun.0 14.02 0.3 0.33 0.33 0.2–24.2 b0.1 b0.0 143.2 Dec.1 4.7 40.5 7.41 6.2 297.2 1.5–25.2 164.5 3.9 21.9 162.3 3.1 8.2 1.2 Dec.9 12.9 Dec.8 91.01 0.2 26.9 0.05 0.5–14.7 16.47 0.4 19.9 21.9 10.43 6.46 0.02 0.3 17.6 0.8 76.9 7.7 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 0.7 8.2 0.2 b0.01 0. 2008 3.06 2.8 0. 2008 4.19 511.8 275.0 92.5 37. / Journal of Geochemical Exploration 136 (2014) 24–39 27 Table 1 Physico-chemical parameters of water samples around the landfill.8 29.2 31.18 0.6 1.1 0.0 315.6–25.48 6.0 72.5 225.39 1.62 7.23 9.55 1.8–22.8 90.2–22.8 144.01 0.6 7.2–26.29 17.17 0.9 27.0 12.2–15.2 153.7 8.1 0.0 478.78 0. 2008 2.9 62.10 0.2 68.29 7.02 b0.1 13.07 1.1 45. 2008 2.05 0.5 2. ID Sampling time Well depth (m) Well screen (m) Utilization T (°C) pH EC (μS/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.1 13.2 30.9 67.24 0.8 17.6 May 2009 1.0 5.05 0.32 0.6 Dec.16 0.10 b0.0 May 2009 1.9 3 0.9 1.2 23.6 74.2 28.0 May 2009 0.9 89.53 1.68 1.004 0.8 102.63 7.2–15.05 0.05 0.7–24.4 119.5 8. 2008 2.5 9.6 17.84 0.1 3.52 7.06 0.0 397.1 8.7 1.8 12.044 0.1 28.4 0.1 57.7 27.01 142.9 54.3 11.5 8.013 0.0 155.040 0.32 0.01 155 24.5 18.5 12.2 3.5 103.7–22.67 0.4 28.7 1.06 312 b0.38 5.01 2.27 0.4 3.2009 May 2009 May 2009 Dec.1 0.2 1.7 4.0 30.3 6.0 92.13 20.9 32.1 0.4 0.02 0.1 −87.45 0.1 b0.5 13.58 0.3–9.67 5.02 0.1 44 178 259 218 159 1.5 13.07 0.8 81.0 644.19 0.04 1.01 932 260 0. 2009 Dec.0 976.11 363.4 10.4 246.1 1.8 7.83 396 961 3644 1316 1369 2930 1671 1332 1076 98 3 115 151 153 106 198 171 73 25 1.25 7.3 11.6 20.0 698.11 0.2 b0.1 1 b0.9 8.82 0.8 63.8 11.01 0.9 105 3 3.0 11.4 151.4 1.6 35.2 37.05 2.09 0.1 7.14 7.4 134.2–6.012 1.0 105.6 61.

058 0. by titration with H2SO4 (0.5 429.04 0.4 52.04 0.0 207.11 1.4 14 24 0.03 356.08 45.0 140.06 0.01 0. 3.0 688.0 203.4 −7.03 0.9 70.0 146.0 549. The wells were purged before sampling and groundwater was collected by pumping.3 23.8 May 2009 0.02 1. In most cases alkalinity was determined on filtered samples in the field.6 10.07 515. Water table depth.0 612.4 25.3 2.2 b0.4 21.4 1.02 0.6 2.8 110.4 0.0 6. only after constant values of electrical conductivity (EC) and redox potential (Eh) had been established.0 328.7 14. 2009 0.31 1. The analytical precision for δ2H is ±1.8 0.3 13.03 1 7. Samples for major anion analysis were collected in polyethylene bottles.1 138. NO− 3 .8 12. with a Finnigan MAT251 after on-line pyrolysis with a Thermo Finnigan TC/EA (Temperature Conversion Elemental Analyzer).5 178 1159 615.2 b0.07 0.1 b0.1 0.01 457 156 1.1 8. 2009 1.2 97.1 30.0 445.6 0.01 501 b0.105 b0.1 Dec.0 1.3 Dec.0 521. although medium-grained sand dominates the aquifers.0 293.5 Dec.0 222.7 May 2009 0. / Journal of Geochemical Exploration 136 (2014) 24–39 Table 1 (continued) Cd Pb Zn Cr6+ Hg As Se NH4+ H2SiO3 CODMn Cl− (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/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 0.1 −7.6 118.5 19.11 0.92 0. China University of Sciences.7 10.1 Dec.6 32.0 0.94 0.07 0.0 155.5 −6.9 0.2 2.8 1358.78 1.3 125.9 1.39 0.1 0. precision ± 5–10%) and minor/trace elements were analyzed using ICP-MS in the Environmental Chemistry Laboratory.008 1.69 1.0 526.0 279.01 712. The measured physicochemical values of water samples from the study area can be seen in Table 1.32 0.0 548.9 126.8 0.46 0.0 81.1 20.30 423 0.005 b0.1 1.012 0.38 All in mg/L (if not specified otherwise) except pH.06 0.0 200.6 −5.0 140.6 164.5 8.06 578.6 b2.7 May 2009 0.04 0.4 0.5 −3. Na+.2 1.450 0.0 184.48 0.7 0.01 860.4 16.9 −5.7 May 2009 0.13 224 42.6 Dec.2 195.01 741.01 628 51.3 22.30 0. The shallow aquifer consists of fine Table 2 Isotope composition for water samples around the Zhoukou landfill (sampled in December 2009).2 b0.1 b0.4 85.85 0.1 b0.6 0.0 118.21 0.6 May 2009 1.0 225.2 Dec.1 b0.2 0.1 1 3. The tested results are shown in Table 2.0 604.4 4.3 1.4 1578 85.034 0.88 0.27 0.030 0.7 May 2009 0.1 0.20 0.2 2.8 145.2 6 7 1.8 637.14 0.43 0. 2009 0. 2009 0.0 12.0 0.7 0.1 0.8 68.6 Dec.6 May 2009 0. Alluvial sediments at the site range in size from coarse gravel to clay. Two alluvial aquifers are present within 0–52 m depth.0 0.7 −6.6 Jun.31 0.2 0.2 15. pH.2 0.2 0.9 F− NO− 2 I− SO2− HCO− 4 3 NO− 3 515.2 110. SO24 −.0 4.9 1.9 25.5 0.006 0.6 May 2009 0.05 0.28 2.41 0.11 612.1 0.68 1521 Hardness TDS (g/L) 1.043 0.4 1.01 705 34.9 2 2 0.7 11.1 86.5 Dec.7 23.05 314 b0. Major anions (Cl−.38 0.0 136.9 32.790 b0.2 −6.2 17. 2010 0.01 0.01 234 101 2.030 0. Most selected sampling points for groundwater were situated near the landfill.0 1.5 0.4 108.3 88.08 0.38 0.2‰. Groundwater flow system The landfill is located on the floodplain of the Jialu River.11 404.0 860.6 0.91 2.0 254.3 46.8 1003. 2010 0. 2009 b0. pH and temperature were measured at the time of sampling.7 −6. dissolved oxygen (DO) and temperature were all measured in the field.9 7.78 2.2 May 2009 0.0 −6.29 0.2 0.01 0.8 630.5 599.4 47.96 1.10 568.8 b1 b1 b1 1.0 244.7 7.0 2.08 305 b0.3 0.7 Dec.4 0.50 b0.4 224. 2009 0.022 0.8 Jun.1 b0.2 0.38 0.1 716.90 0.4 0.58 0.4 1.1 1.004 b0.18 0.01 556.570 0.7 19.016 0.0 −7.99 1. 2009 0.3 Jun.02 0.0 713.55 75.6 b0. A fresh sample tube was used for each piezometer to prevent cross contamination.7 Dec.0 0.6 0.0 357. All samples were filtered through a b 0.8 813.04 0.2 0.9 131. 2009 0.0 3.01 608 85.02 0.58 0.004 1.0 75.0 19.5 2.6 1.1 4.21 0.2 38. K+.2 5.3 2.02 0.3 2.6 1 1 14.101 0.1 b0.2 0.0 292.1 22. Results and discussion 3. The δ18O and δ2H values were measured relative to international standards that were calibrated using V-SMOW (Vienna Standard Mean Ocean Water) and reported in conventional δ (‰) notation.5 31.0 0.0 342.0 227.4 0.59 1.5 11 1.1 −6.45 0.0 289.81 2045 b0. 2010 3. Stable isotope values of δ18O and δ2H were measured by mass spectrometry.9 25.2 1.0 72.024 b0.0 242.6 2.4 – – – – 0.2 2. in the State Key Laboratory of Geological Processes and Mineral Resources.7 0.01 475 b0.0 0.0 0. 2009 0.3 24.5 536.6 Dec.02 0.46 0.1 0.04 342 41.2 39.0 154.08 0.7 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. 2009 0.0 771.7 May 2009 0.02 0.9 1.8 167.04 0.2 93.6 136.2 17.1 0.09 528 20.5‰ and for δ18O is ±0.3 1.81 0.8 Dec.05 0.6 52.4 1.50 0.1 0.5 −63 −59 −51 −34 −57 −53 −36 −55 −60 −62 −55 −58 −64 −71 −59 −59 −52 .0 650.0 605.48 0.16 168.91 1.2 1.990 0.1 b0. 2009 0.3 0.5 May 2009 0.5 0.0 249.6 May 2009 0.1 Jun.106 0. 2009 0.71 0. 2009 0. while major cations (Ca2+.04 634 1.27 1.1 b0.22 N).6 0.71 0.66 0.02 0.5 0.0 995.30 b0.39 0.1 0.0 11.9 4.004 0.59 725 43.20 321.4 2.36 1.005 b0.7 209.2 104.077 0.5 0.011 b0.8 12.5 May 2009 0.8 Dec.6 48.7 −6.008 0.19 0.01 1870 0.0 2.32 – – – – 19.1 249.0 131.05 0.7 0.11 0.1 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 2.9 1.7 Dec. and acidified to pH b 2 with 6 N HNO3.9 −6.0 719.1 19.3 20. EC.6 Dec.9 1.0 126.003 0.0 782.84 0.9 2.5 0. 2010 0.2 −2.83 0. tightly capped and stored at 4 °C until analysis.6 3. Mg2+.018 0.9 2.2 0.1 1. precision ± 5–10%) were measured using ion chromatography (DX120).2 20.6 30.0 745.9 6 7. Han et al.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 b0.0 10. turbidity.0 220.026 0.8 0. Eh.8 −6.3 39.2 26.01 0.01 368.83 0.64 0.28 D.1 0.0 9.0 487 4.00 1.11 0.0 424.63 b0.3 149.0 19.1 0.02 0.35 0.0 484. 2009 0.2 0.8 0.0 305.45 μm membrane filter to separate the particulate from the dissolved fraction.1 3. School of Environmental Studies.67 0.9 2.12 1.1 0.47 0. Water sample Well depth (m) δ18O (‰) δ2H (‰) 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 −7.2 143.680 0.3 187.69 0.1 4.6 108.01 309. China University of Geosciences.4 1.4 0.06 0.170 0.1 25.87 1.012 0.8 1.4 17.0 82.1.98 4.0 177.2 1.03 0.6 1.118 b0.02 792.0 20.36 b0.8 150.63 6.02 0.0 9.9 1.09 1.1 0.1 4.7 0.9 54. 2009 8. Samples for cation analysis were preserved in acid-washed polyethylene bottles.

D. The distributions of δ2H and δ18O in surface and groundwater samples are similar. The depth to groundwater in this well is about 42 m below the ground surface. leachate = 40. The local water table gradients below and around the landfill are likely to differ from the regional gradient.. suggesting that they may have more influence on local groundwater during the summer season.5 to − 2.1 to 0. 2012).7°C.11 g/L.0′E) some 200 km NW of Zhoukou city.1‰ for groundwater and −56 and −6. Piper plots show that the water type is closer to HCO3-type.2. and their thickness becomes slightly thinner towards the south where the sediments become more clay rich.iaea. The rainfall data were taken from the IAEA network (http://isohis. org). and sewage water (ZC and ZD) is Na-HCO3 · Cl or Na · Mg · Ca-HCO3 type with less than 1 g/L TDS.94) is based on δ18O and δ2H values of the average monthly rainfall monitored between 1985 –1992 at Zhengzhou station (34°43. which is approximately parallel with the GMWL and LMWL. indicating a colder climate during recharge. The local meteoric water line (LMWL) represents the monthly averaged isotopic composition of long-term precipitation at the monitoring station Zhengzhou.7 mg/L. and the Jialu River. Recharge to the alluvial aquifers consists of infiltration from precipitation. CODMn. 1986) with a TDS concentration ranging from 0. and hence more beneficial for usage.81 g/L. 3. Fig.94.29 g/L) . 113°39. 2002). as landfills usually have different hydraulic properties compared to the surrounding area. and evaluate any possible evaporation (Table 2).3 δ18O + 2. the saturated zone sediments are coarse-grained.2. 3. Stable isotopic composition of water samples in the study area (relative to VSMOW). Surface waters are generally Na-HCO3 · SO4 or Ca-HCO3 · Cl type (according to the classification of Stuyfzand.62 g/L TDS.3m is embedded in this silty clay. the amplitude of the seasonal variation between wet and dry periods ranges from 0. As Zhoukou city is located in the south of the Yellow River alluvial fan. 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. can be regarded as an aggregative indicator reflecting the extent of groundwater pollution by organic and reducing inorganic matter (MEP. and/or evaporation of groundwater prior to/during recharge. 3).6 m. turbidity can reflect the degree of contamination or leachate influence in different water bodies. which creates a potential pathway for rapid transport of contamination. Groundwater discharges to small streams. δ18O for surface and groundwater is shown in Fig.3. Stable isotope compositions The δ18O and δ2H stable isotope composition of groundwater can be analyzed in order to understand the recharge origins and circulation of the groundwater.. being part of the Global Network of Isotopes in Precipitation (GNIP). The hydraulic gradient of the shallow groundwater is approximately 0. probably due to drawdown caused by pumping in the deep layers. Groundwater levels in May 2009 were generally lower than in December 2009 (after the wet season).7) in the winter season and high turbidity (0.0014 and locally near the landfill. 2010). mean value of 5. groundwater discharges to the Jialu River at all times. and in May 2009 and June 2010 were found to be slightly more Na and Cl-rich. Most water samples are distributed along an evaporation line (Fig. The investigated Zhoukou landfill with a thickness of 9. apart from the two shallow aquifers. / Journal of Geochemical Exploration 136 (2014) 24–39 sand and silty sand at a depth range of less than 30 m. 29 3.2–90.08– 46. or pumping of groundwater in the areas outside the landfill. Groundwater sinks include discharge via evapotranspiration into the shallow soil zone. Fig. Sewage water and leachate samples recorded a much higher turbidity of 79. 4). Groundwater was characterized by low turbidity (0.7 m.2‰ for surface water. Han et al.46 to 2. with a mean value of 1.3.2′N. These coarse-grained sediments are common throughout the Huaihe River Basin and are typically associated with groundwater pollution (Qu.61 to 8. According to the monitoring data. (expressed in oxygen mg/L). mean value of 0. A wide range of electrical conductivity values (396–approximately 4000 μS/cm) indicate presence of either contamination by leachate (expected to have high salinity). Another silt and silty clay layer 20 m thick occurs between the shallow and deeper aquifers. Low permeability silty clay of 11 m thickness exists above the shallow aquifer. and is a major layer for irrigation extraction in the local region. To some extent. which is likely to be an aquitard. The presence of relatively high CODMn (range of 0. This is common in the deep aquifers of northern China. Deep groundwater (from ZK. A local water table mound has been observed at the Zhoukou Landfill (water levels are higher than the surrounding areas). A plot of δ2H vs.1–1. TDS concentrations of groundwater ranged from 0.9. Inorganic macrocomponents in surface and groundwater 3. Groundwater samples collected in December 2008 and December 2009 were found to be Ca · Mg-HCO3 (Cl) type. Hardness values ranged from 142 to 2045 mg/L as CaCO3. The thickness of low permeable silty clay underlying the landfill is approximately 1.85 g/L. Stable isotopic compositions of groundwater range from − 7. Physico-chemical characteristics of water samples The temperature of all water samples ranged from 7. δ2H = 7. and consists of fine sand. and leakage from irrigation return flows near the landfill. r2 = 0. Landfill leachate (ZE) is Na · Ca · Mg-HCO3 · Cl · SO4 type with 1.1 with a mean value of 84. higher than this.96 g/L with a mean value of 0. rivers and channels.3 m to 8. and out-flux of groundwater to surface water in downstream areas.64 to 0. one deep well (ZK1. The mean δ2H and δ18O values are −56 and −6. With the exception of flood periods (where surface waters recharge the groundwater). well depth of 300 m) has lower values of δ2H and δ18O. n = 11 from Jan. and is subject to evapotranspiration. 3. respectively. The water table monitoring data shows that groundwater levels in the study area varied from 2. The groundwater was characterized by the pH values from 6.9–17. Groundwater salinity in the summer season (mean TDS concentration of 1. A wide variation in groundwater values from the study area on the right side of the GMWL was observed.9) in the summer season. The global meteoric water line (GMWL) corresponds to Craig (1961) and the local meteoric water line (LMWL. wetlands.2 m depth. in the winter season compared to summer (Fig. where much of the groundwater was recharged during the late Pleistocene (Currell et al. This could be due to higher infiltration capacity and preferential recharge at the site. 1) reaching 300m in depth was also investigated for hydrochemical analysis.7‰ for δ18O and from −71 to −34‰ for δ2H.6 to 22. The aquifers are widely distributed across the study area. and near the LMWL. The deeper aquifer occurs at a depth range of 45–52 m. artificial extraction.1. to Dec. In order to make comparison with groundwater hydrochemistry at different depths. which has a water table depth of 2–3m.1. indicating that surface and groundwater have similar origins (rainfall).3 mg/L) in the collected groundwater samples near the landfill indicates the threat of severe contamination of groundwater.

5. . (c) CODMn and As. Hardness. (d) Fe. 4. (a) NO− 3 and Hardness. TDS. CODMn. Ca and Mg have obvious decreasing trends with the increase in distance from the landfill center. which could be attributed to the rising water table and subsequent mixing of leachate with groundwater water nearby. Mn. Cl−. Mn. As. Han et al.97 g/L). indicating greater amounts of leachate generated in the Zhoukou landfill in summer. Fe. / Journal of Geochemical Exploration 136 (2014) 24–39 Fig. (b) TDS. 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. − − 2− Fig. F . Ca and Mg. Variations of some chemical parameters with distances away from the Zhoukou landfill center.30 D. Some evaporative effects in summer may also be responsible for the higher TDS contents. Cl and SO4 . Piper diagram showing the hydrochemical composition of water samples around the Zhoukou landfill aquifers.

5% (mean value of 55. collected in May 2009 and Dec.2009. Three groundwater samples collected from the well ZKN (Table 1). b′).3.D. TDS. 5a. Major anions A wide range of major ion compositions were observed. Mn (d. Additionally. respectively. 6. a′). Concentration contours for the Cl−(a. It can be seen from these maps that the concentration of Cl. 3.6%. f′) of groundwater samples from the shallow aquifer (b30 m depth). These indicate that the landfill contributes salinity. e′). There is a definite attenuation of chloride in groundwater down gradient of the landfill (Fig. respectively. and NH4 (f.8–71. / Journal of Geochemical Exploration 136 (2014) 24–39 31 − 2− + Fig. HCO− 3 and Cl accounted for 18. 5.c). hardness and CODMn to the adjacent groundwater. of total anions. SO4 (c. exceeded the proposed drinking water quality standards for chloride. The concentration contours of several selected ions and elements in shallow groundwater are shown in Fig. similar to surface water (46. c′).6%) and 11.b.3%). . as shown in − the Piper plots (Fig. NO− 3 (b.8–78. hardness and CODMn of groundwater showed an obvious decreasing trend with increasing distance from the landfill center (Fig. 6a and a′). Units are in mg/L. 6.d). Han et al.9% (mean value of 26. NH4 and Mn (common characteristics of leachate) decline away from the landfill. 4).3% and 28.2. respectively). and TDS showed a decreasing trend with increasing sampling depth (Fig. d′). F (e.

and so aerobic oxidation of organic matter is probably still a major process.68⁎⁎ SO2− 4 HCO− 3 NO− 3 F− Hardness TDS 1 −0.81⁎⁎ 0. the majority (83%) of groundwater samples collected in May 2009 were characterized by F− concentrations greater than 1 mg/L. Gong et al. 1995). Fe. Groundwater fluoride concentration showed a strong correlation with sulfate (SO2− 4 ) concentration (Table 3).21 0.16 0.36⁎ 0. 2010). hornblende) were detected in Funiu Mountain area (Gong et al.26 0.48⁎⁎ 0. 2003). and groundwater with low nitrate concentration (b 0. (2011). Han et al.01 0.. indicating little or no heterotrophic denitrification. Na+ 1 0.2 mg/L) was distributed near the landfill (e.11 0. the F contents of groundwater are locally higher than 2 mg/L (even up to 4.01 0. if the landfill leachate is a significant source of alkalinity. ZD.19 mg/L at the well DW09) in this study area.63⁎⁎ 0. fine-grained sediments and the relatively stagnant groundwater flow in this region are more likely to result in the fluorine enrichment (Gong et al.48⁎⁎ 0..01 0. and nitrate (NO− 3 ) concentrations ranged from 0.37⁎ −0. − There is no significant negative correlation between NO− 3 and HCO3 .08 −0..08 0.05 1 0.g. and Ca high near the landfill site.87⁎⁎ 1 .52⁎⁎ ⁎⁎ Correlation is significant at the 0.54⁎⁎ −0.45⁎⁎ −0. and the extent of mixing with the leachate. ZC. Long-term ingestion of high-fluoride groundwater is the major reason for endemic fluorosis in this area (Gong et al.19 mg/L (mean value of 0.51⁎⁎ −0.49– 0.01 0. ZG10. indicating that F− may be more susceptible to migrate in the aquifer during the summer.09 0. Fe(OH)3.60⁎⁎ 0.g. EC pH Ca2+ Mg2+ Na+ K+ CODMn Cl− SO2− 4 HCO− 3 NO− 3 − F Hardness TDS EC pH Ca2+ Mg2+ 1 −0.3 mg/L) in the surface water samples. 2010). This is likely due to a lack of denitrifying bacteria.11 0. ZE). it also can be seen from the hydrochemical isolines map (Fig. decreasing as groundwater moves away from the landfill.9 mg/L (mean value of 13. which would otherwise continuously remove nitrate from the aquifer (Mohamed et al. 2003. Biochemical reactions can produce ammonium (NH+ 4 ) in groundwater.g.56⁎⁎ 0.24 0. Cl−..17 0. Kim et al. phosphatic fertilizers may be responsible for high concentrations of fluorite in groundwater (Li et al. Most groundwater is characterized by dissolved oxygen (DO) of more than 1 mg/L. The existence of this long-term condition in the region indicates that fluoride had a geochemical source present in the aquifer before the installation of Zhoukou landfill.20 −0.87⁎⁎ K+ 1 −0.05 1 −0. a condition that affects human health by causing damage to bones and joints (e. ZG10.. SO4 et al. only well ZB exceeded the maximum acceptable level. with the presence of ammonium and elevated nitrite at Z40.. indicating organic pollution providing electron donors (Chapman. In terms of changes in solute concentrations along the 2+ are groundwater flowpath (Fig.55⁎⁎ 0. ZKW and Z16. Among the groundwater samples collected in December 2008. (2010) and Currell et al. consistent with the findings of Cai (1999). The F− concentrations in 33% of groundwater samples exceeded the drinking standard of 1 mg/L. / Journal of Geochemical Exploration 136 (2014) 24–39 Fluoride (F−) concentrations in groundwater range from 0.g.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 .78⁎⁎ 0.5). In addition.7 mg/L) and nitrate could not be detected in the sewage water nor the leachate (e. Common F-bearing minerals (e.65⁎⁎ 1 −0. Although there is a big variation of F concentrations in May and December 2009.1 to 42. 2004).14 −0..46⁎⁎ 1 0.93 mg/L) and are from 0.16 0. Nitrate reduction potentially occurs at the mixing zone of landfill leachate and shallow nitrate containing groundwater.. ZKE.32 D. as opposed to any point source nitrate contamination from the landfill site. TDS. 2010).g.30 0.09 −0. In this study. 2004). 2009).. releasing bicarbonate and nitrogen gas to the system as byproducts (Babiker et al.. MnO2.23 −0. Wilson NO− 3 . has relatively high NO− 3 and F concentrations.58⁎⁎ −0.57⁎⁎ −0.58⁎⁎ −0.. Therefore.74⁎⁎ 0. Nitrate reduction can cause disappearance of nitrate with depth (Postma et al. Many hydrogeochemical investigations show F concentrations of groundwater in Xuchang and Pingdingshan area. 1992). Groundwater with high nitrate concentration (even up to 487 mg/L at DW09) was distributed in the downstream area of the landfill.06 −0.05 level. This indicates that local agricultural activities (e. In the present study. ZE). ZD.g.10 0.11 0.24 1 0. 6e. 1991).32 CODMn 1 0. which is located in the southwest of Zhoukou city and about 200 km away from Zhoukou.g. 2009. Shui and Zhang.40⁎ 0.01 level. ZKN). which use the oxygen from nitrate to generate energy from organic carbon.82⁎⁎ 0. also potentially affecting the shallow monitoring wells (e. 2007).66⁎⁎ 0.06 0. the oxidation sequence for the major chemical components at neutral pH can be in the order: O2.61⁎⁎ 0.12 −0. The majority of groundwater samples in this study were collected from the shallow aquifer (less than 30m depth). groundwater collected from wells used for − agricultural irrigation and domestic use.54⁎⁎ 0. while groundwater Cl− concentrations show an obvious decreasing trend with increasing distance from the landfill center Table 3 Pearson correlation matrix for major ions and pH.46 to 2.04 −0. Apart from the geological background source. range from 1 to 2 mg/L. and relatively lower F− concentrations (0.42⁎ 0.10 −0. However. Mn.27 −0. indicating the partial nitrification of the ammonium plume due to infiltrating oxic water.15 −0.86 mg/L) were detected in the sewage water and the leachate (e. NH+ 4 .66 mg/L (mean value of 1.33⁎ −0.03 0. Additionally.19 −0. 2− and CO2 (van Breukelen. Surface water NO− 3 concentrations ranged from 0.09 0.17 0.71⁎⁎ 0. the use of N-fertilizers with precipitation infiltration or irrigation return flow) are the primary cause of the extensive groundwater nitrate contamination (Zuo et al. and there were no wells that exceeded this standard in December 2009. fluorite. 6).33⁎ −0.. Based on the theory of Gibbs free energy. However.60⁎⁎ −0. respectively (van Breukelen. indicating there is the aerobic aquifer environment.60⁎⁎ 0.10 0. which close to the study area.02 to 4.37⁎ 0.00 0.54⁎⁎ 0.e′) that F− shows lower concentrations surrounding the landfill.42⁎ 1 0. ZG11) in this study.09 0. 2003). high F groundwater (N1 mg/L) was observed in groundwater with high pH values (N 7.68⁎⁎ Cl− 1 0.60⁎⁎ 0.45⁎⁎ 0.18 −0.55⁎⁎ 0.26 −0.55⁎⁎ −0..14 0. EC and TDS of the groundwater around Zhoukou landfill. 2012). ⁎ Correlation is significant at the 0.g.72⁎⁎ −0. ZG11.46⁎⁎ 0. indicating that denitrification is likely a dominant redox process at the downstream fringes of the plume. this could indirectly lead to greater levels of mobilization of fluoride from natural geological sources (e.62⁎⁎ 0.56⁎⁎ 0.39⁎ 1 0.12 0. ZC. 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. dental and skeletal flourosis) (Cauley and Murphy.

Scatter plots of Ca–Mg (a) and Fe–Mn (b) concentrations versus pH of groundwater samples. 1995).g. Han et al.5 and 8. (c) Zn.6 mg/L (mean value of 69. 5b and Fig.0 mg/L (mean value of 175. where the shallow aquifer is composed predominantly of fine sand. 6). 6a. respectively). SO4 and F concentrations 2− do not follow this trend (Fig. 7). respectively (Table 1. 5d). Cl and NO3 . Major cations Na and Ca are the most abundant cations in the groundwater with concentrations of 30. discharging domestic waste water into aquifer locally) and geo2− and Cl− logical background. it would appear that pH is not the only factor controlling the distribution of Fe 3. (a) Ca and Mg. Fe and Mn variations in water are mainly controlled by oxidation–reduction conditions and acid–alkali balance (Virkutyte and Sillanpää..D. (0. 3.3. In this study the lowest Fe (0. Fig. Additionally. Ca and Mg in groundwater are characterized by an obvious decreasing trend with increasing distance from the landfill center (Fig.7–212. concentrations will increase (Pitt et al. This indicates that higher concentrations of these cations may be caused by leakage of landfill leachate into the groundwater. indicating that the combined solute load is high near the surface due to the combination of anthropogenic influences (agriculture and landfill leachate).3.. / Journal of Geochemical Exploration 136 (2014) 24–39 33 − − Fig. 7.6 mg/L) and 13. fertilizer utilization.9 mg/L). similar with other ions (Fig. Pb and As. However. 1999). The highest concentrations were found at depths of less than 30 m. the highest concentrations of Ca and Mg were found within the shallow aquifer (Fig. 4).9. . indicating that pollution of NO− 3 . 2006). SO4 and F− may be due to local anthropogenic activities (e. (d) Fe. a′). rather than landfill leachate.. 8. SO4 concentrations in groundwater are characterized by a decreasing trend with increasing sample depth. NO− 3 .05 mg/L) and Mn Fig. The high Mg concentrations around the landfill may result due to industrial waste like cosmetics. (b) SO2− 4 . Characteristics of some chemical parameters with well depth around the Zhoukou landfill.4. Fe and Mn High contents of dissolved Fe and Mn can be produced by reducing conditions generated in the landfill. Mn and TDS. 8b) were found in the groundwater with the highest pH (8.02 mg/L) concentrations (Fig. Fe and Mn can be oxidized by anaerobic bacteria and under low pH conditions.2–872. 2− − (Fig. 7a). groundwater NO− 3 . cement and textiles are being dumped into the landfill (McBean et al.3.

001)–0.004)–0. 7c).1 mg/L.3. Mn. which were significantly higher than the maximum allowable concentration (0. Se and Hg During the sampling campaigns. Aluminum (Al) levels ranged from b0. showing that the highest concentrations of As were observed in Fe-rich environments. Away from the landfill. 3. Consistent with the findings of Varsányi et al. The Fe and Mn concentrations also showed an obvious decreasing trend with increasing distance from the landfill center (Fig. and NH+ 4 decrease away from the landfill.065mg/L. 7c). 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 landfill. where the pH was slightly alkaline (7. ZG10. near-neutral pH conditions.7). 9b). Se and Hg were found in very low concentrations (up to 7. and Mn.038 mg/L.5. Cd and Cr concentrations ranged from BDL (b0. The highest concentrations of Pb were observed in the SO2− 4 poor environments (Fig.02 to 1. Fig. 11.008 mg/L and BDL (b 0.9.2 μg/L and 0.01mg/L) according to the National Chinese guidelines. respectively. 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. 6) and with increasing sample depth (Fig. Scatter plots of Fe–Mn (a) and As–Pb (b) concentrations versus SO2− 4 concentrations of groundwater samples. photographs. which are toxic to all forms of life at this level (Al-Yaqout and Hamoda. Lead (Pb) concentrations in the groundwater ranged from BDL (b0.0 and 14. respectively. It can be seen from Fig. The presence of zinc in the groundwater indicates that the landfill may be receiving waste batteries and fluorescent light bulbs and is a cause for concern with regards to plant and aquatic life (Al-Yaqout and Hamoda.003 mg/L. groundwater As concentrations were characterized by an obvious decreasing trend with increasing distance from the landfill center (Fig.052 mg/L) observed in Fe-rich (Fig. The Mn concentration in 76% of all groundwater samples exceeded the National Chinese drinking water standard of 0. indicating higher concentrations of Fe and Mn caused by infiltration of reducing leachate. who determined that Mn has a strong correlation with sulfates resulting due to sulfide oxidation. 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. Possible sources of lead contamination may be batteries. 9b). / Journal of Geochemical Exploration 136 (2014) 24–39 Fig. 2003).01 mg/L were also found in some wells. (2004).052 mg/L) of As. The zinc (Zn) concentration ranged from below the detected limit (BDL) to 0. for example. Mn. Acidity in leachate causes lead to be released from refuse. 3. 5c) and increasing sample depth (Fig.0 mg/L. there will be the effects on absorbed concentrations due to the low pH and Eh beneath the landfill.3. As the concentrations of Fe.024–0. landfill leachates contain only modest concentrations of heavy metals as the metals are subject to strong attenuation by sorption and precipitation (Christensen et al. with the lower concentrations not exceeding the WHO and NC . In general. Variations of groundwater level in different seasons may change the redox environment in the aquifer. 2001).2 μg/L. as an extremely high concentration of Fe (4. As. Zn and Pb concentrations of groundwater samples were also characterized by an obvious decreasing trend with increasing sample depth (Fig.6 and was observed in well ZKN in December 2009.038 mg/L occurred with a pH value of 6. the mean concentration of As in the remaining water samples was 0. and Mn at landfills. which is below the maximum allowable concentration. 9b that low sulfate corresponds to high Pb. In contact with the process of reducing leachate from the landfill. the typical major cations will be preferred on the exchange sites.002) to 0. respectively) without exceedance of the NC standards. 11). NH+ 4 near the landfill (Deutsch. In general. 2003). Fe.6.. Additionally. Fe and Mn have a negative correlation with SO2– 4 concentrations in all groundwater samples (Fig.34 D. 9. Z16 and ZKE recorded As concentrations of 14. old lead-based paints and lead pipes disposed at the landfill. 9a) which is not in agreement with Olías et al. 1997). the highest Pb concentration of 0.8 mg/L) was found in well Z16. the Fe concentration in the groundwater strongly influenced the distribution of As with the highest concentrations of As (up to 0. 10) and SO2− 4 -poor environments (Fig. manganese and iron oxyhydroxide minerals in the subsoil will be more soluble in a reducing environment than in the natural oxidizing environment (Deutsch. (1991).1 mg/L with 21% of groundwater samples exceeding the WHO and NC standards (0.02 mg/L. ZKS had high concentrations (0. Han et al. Cation exchange with clays may be an important process responsible for the high concentrations of NH+ 4 . 7d). 5d and Fig. Pb concentrations of N 0. 10. Scatter plots of Fe versus As contents. If these values are excluded from the dataset. 1997). Additionally. with the majority of samples recording a low concentration that did not exceed the World Health Organization (WHO) and National Chinese (NC) standards. Elevated levels of major cations present in groundwater may partially result from cation exchange reactions driven by the high levels of Fe.2 mg/L). Heavy metals of surface and groundwater Generally.

partly because concentrations in the sewage water and the leachate are often low. 12. 2011). Fig. standards.. Generally. 11. (b) and (b′)—component score plot for the water samples collected in May 2009 and Dec. 1991). heavy metals do not seem to constitute a significant pollution problem at the landfill site.2009. . indicate that there will be some concerning human health risks caused by high intake of Cd (Ikem et al. respectively.D. / Journal of Geochemical Exploration 136 (2014) 24–39 35 Fig. 11) showed that these contaminants are characterized by higher concentrations in May 2009 and lower concentrations in December 2008 and December 2009. respectively. 2002) and Cr (VI) (Wedeen and Qian. showing the plots of variables and loadings (a) and (a′)—Principal component loading plot for the water samples collected in May 2009 and Dec. Variation of contaminant concentrations in the selected monitoring wells during three sampling campaigns. and partly because of strong attenuation by sorption and precipitation in the sedimentary aquifers (Xie. The high concentrations. Seasonal variations of the major heavy metals in groundwater (Fig. however. Results of the principal component analysis (PCA) for major chemical components in groundwater samples surrounding the Zhoukou landfill site.2009. Han et al.

In space variables. Chloride ion was selected as the conservative tracer because it is generally not subject to undergo any physico-chemical reactions (e. Mg. respectively. and HCO3 in May. DW23.c′) near the landfill due to sulfate reduction. SO4 and HCO3. HCO3 . DW25. − − F .3% of total sample variance (43. Groundwater recharge in the study was estimated of ~36 mm/yr (Qu.00033 (Qu. 12b. with a uniform horizontal 20 m grid cell size with thickness of 2–3 m (Fig.. Han et al. Fe. Cl and TDS in the two sampling periods.0014. K. 13. the sulfate concentration in the landfill leachate has generally lower values.. 2013). There is also a notable decline in sulfate (Fig. 1992). t is time. NO3 . Mn. 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. 2009) have been analyzed separately. Dx. 2010). seen in Fig. including leakage of landfill and fertilizer input through irrigation infiltration along the groundwater flow paths surrounding the landfill. ∂t ∂x ∂z ∂x ∂z where C is dissolved concentration. vx. NO3.. The effective porosity value ranging 5–15% is anticipated for the aquifer made up of fine sand in this site. ZKS. Although groundwater flow in the aquifer is essentially horizontal from the area north of the landfill to the area south of the landfill (Fig. DW18 with high score N+4 in PC2 is strongly associated with nitrate pollution from agricultural practices.3% for PC1 and 25. and all analytical values less than dbl are replaced with zeros. the leachate pollution and the water-rock interaction give high scores in PC2. The total number of components from PCA can indicate potential sources of groundwater salinization and provide insight into the interpretation of the data. 12a. In this study. 2013).g. ZKW). 12a. b′). Group 1 can be described by mineralization of groundwater by water-rock interaction. Fig. 1999). Mg2+.and medium grained sand are in the range of 11–12 m/d (Qu. 12a. The values for hydraulic conductivity from 12 pumping tests in the fine. The bottom boundary of the model is restricted by the depth of available investigation boreholes in this site and is assumed no flow. The top boundary of the cross section model receives recharge from precipitation. having great influence on groundwater quality around the landfill site. and the rate of leachate entry to the aquifer was estimated of 60–280 mm/yr (Song et al. SO4. Based on the measured water level contours in December 2009. Based on the analysis of variable loadings on PC1–2 in Fig.b′). The axis PC2 opposes Fe. and the leachate pollution plays the dominant role in controlling groundwater quality surrounding the landfill site (e. a′. The cross section was vertically discretized 19 layers in total.2009. 2005) was used to simulate the groundwater flow. The contaminant transport model was used to assess how landfill leachate may migrate into the upper sand unit.0% for PC2) in May 2009 (Fig. Therefore.5. three groups of samples can be identified. The investigation of organic contamination in shallow groundwater surrounding Zhoukou landfill showed that there is no inflow of polluted groundwater into the river and sewage ditch. Each of the silt/clay and sand units shown in Fig.36 D.. SO4 . 1999): ∂C ∂2 C ∂2 C ∂C ∂C ¼ Dx 2 þ Dz 2 −vx −vz . DW18. 13a). The computer code MODFLOW-2005 (Harbaugh. 6c. the PC1 factor takes high positive loading for the most chemical components in groundwater except for NO3. Dz are dispersion coefficient. ZKE.1. Contaminant transport model To better distinguish the hydrogeochemical processes controlling the groundwater hydrochemical composition. 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. 12 shows the loading plot and substantiates that the first component is mainly related to Na. K+. adsorption.. a′.7% of total samples variance (46.g. In order to investigate the extent of migration of the landfill leachate into the sand aquifer and the role of the clay/silt layers. Mn.2% for PC2) in December 2009 (Fig. principal component analysis (PCA) (a common multivariate statistical method) was applied to the groundwater samples. 1). The 2D advection dispersion equation is written as (Zheng. the multi− 2− − variables include Ca2+. precipitation. chloride can be used to study dispersion and dilution of a contaminant plume. The flux flowing in/out in the lateral boundaries of the sand aquifer were estimated according the geometry of the boundary and the regional hydraulic gradient. No other point sources or distributed sources of chloride ion were simulated in this study. 2010). Z34). and the computer code MT3DMS (Zheng. or whether the deeper sand unit could be contaminated. and may not maintain a degradation potential equal to iron reduction. a reliable hydrogeological conceptual model was established. Fe. vz are velocity component in X and Z direction. Based on the data on . The calculation was carried out with SPSS 16. Principal component analysis 3. Compared with the ambient groundwater. and TDS in groundwater samples (the dataset shown in Table 1). / Journal of Geochemical Exploration 136 (2014) 24–39 3. was used to simulate the two-dimensional advective-dispersive transport of a conservative solute down gradient from the landfill site. The landfill body is the main pollution source for groundwater contamination in the study area. 12 a′. NH4 and F that show a negative loading. the hydraulic gradient near the landfill is approximately 0. the zone of leachate contamination beneath the landfill has penetrated downward through the entire upper sand aquifer thickness to a depth of 13–25 m (Han et al.4% and 9. The elevated concentrations of dissolved Fe and Mn in groundwater near the landfill indicate these elements mainly mobilize under reducing conditions from landfill leachate.g. This indicates that the vertical flow is also a primary influence on the distribution of contamination zone. two significant components were identified to represent 68.. SiO2 and As variables were not included because they are frequently below the quantification limit. 2010). However. there are different loadings with opposite trend on these chemical components in different sampling periods. the irrigation return flow and waterrock interaction make large contributions to groundwater quality towards the downgradient area (e. After autoscaling..5% for PC1 and 27. a chloride transport model along a cross section was constructed.1% of the total variance. Pb. Na+.0002 0. 2009.5. The 3. and 73. and biological degradation) in the aquifers (Christensen. In summer season. respectively. Mn and NH4 to NO3. Cl . Among these water samples. 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. Other conservative solutes are expected to behave in a similar fashion and could be simulated. 2012). Ca. In this context. 13b). 13a was discretized into 2 to 4 model layers. and usually it is characterized by high concentrations in leachate and leachate-contaminated groundwater near the landfill. Al. and the contaminated river and waste water from sewage ditch does not generally recharge the groundwater body (Han et al. the different factors controlling on groundwater hydrochemical components can be proposed (see Fig. The N-S cross section was chosen to construct the contaminant vertical transport model (Fig. Model geometry and parameters Based on the analysis of groundwater hydrochemistry and hydraulic dynamics in the study area. and to Fe. The third component takes into account only 13. and was not considered in the present analysis. SO4.b). whereas the second component is mainly related to F. shown in Fig. NH+ 4 .4. 2011). The water samples collected from the shallow aquifer (13–25 m depth) in different time periods (May 2009 and Dec. In the winter season. due to the groundwater level fluctuation and redox environment variations. given data on influent and background concentrations. A representative value of the horizontal hydraulic gradients in the regional aquifer covering the landfill site is in the range of 0. and NH4 in Dec.

14. / Journal of Geochemical Exploration 136 (2014) 24–39 37 Fig. . The effects of uncertainty in vertical hydraulic conductivity and effective porosity are shown in Table 4. Although longitudinal dispersivity of 10 m and 100 m can produce chloride concentration of ~1000 g/L at the end of 2010. in a range of 41–112 m/yr.7 0. 10 and 100 m. 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.3 23.7 22.001 0.4 Fig. respectively. For 100 m of dispersivity. Several model runs are made with longitudinal dispersivity (αL) as 1. The values of vertical hydraulic conductivity of the clay/silt layers were assumed to be in range of 0.05 7.1 Travel time (yr) Effective porosity Travel time (yr) 110. The simulated values considered reasonable for horizontal and vertical transverse dispersivities in the sand aquifers are 10 m (longitudinal) and 0. 14). Longitudinal dispersivity of 1m resulted in a maximum value of chloride concentration of ~500 mg/L at the end of simulation. The travel time is calculated by the particle tracking software MODPATH (Pollock. effective porosity (n) and hydraulic conductivity (K).15) also decreased the travel time to about 1/3 of the base value.0001–0. which may not be anticipated considering the operation history of the landfill. Reducing the effective porosity to 1/3 of base value (0. hydraulic gradient (i). 13. The simulated chloride concentration show significant different break-throughs in the upper aquifer beneath the right lower corner of the landfill (Fig.0 13.0 0. Table 4 Average travel time under different Kv and effective porosity along the pathlines beneath the landfill to the top of upper aquifer. 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. Kv (m/d) 0. No information is available about the hydraulic conductivity of the silty clay and silt units at this site. the shape of the break-through is significantly different. the travel time through the pathlines starting the bottom of the landfill to the top of upper aquifer serves as a useful response for model sensitivity analysis.0001 0. 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. Han et al.4 0. Given the operation time of the landfill since 1998. 1994) and is a sensitive to the hydraulic conductivity and effective porosity. 3.2.1 14.5. values of the average groundwater seepage velocity (v) were obtained as v = −Ki/n. Concentration break-through in the upper aquifer beneath the right lower corner of the landfill for different dispersivities. the concentration reached about 760 mg/L only after 2years of simulation. For the purpose of modeling vertical migration of contaminants in the silt/clay layers.01 m/d. (a) Model geometry for the transport model and (b) finite difference grid and boundaries for the flow model. The model is run 13 years to represent the operation time of the landfill since 1998 to 2010.1 m (vertical).01 0. mechanical dispersion is neglected and only advection and diffusion were considered. 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.15 22. which is much lower than chloride concentration observation. Vertical transverse dispersivity is assumed 1% of the longitudinal dispersivity.D.

Under low pH and Eh conditions.35 meter difference between spring and summer water table caused a higher magnitude of vertical gradient over summer and autumn. This study of the isotopic and hydrochemical composition of surface and groundwater around the Zhoukou municipal landfill has been conducted to better understand the extent of contamination from landfill leachate. without any bottom liner and leachate collection and treatment system. Conclusions and implicated measures The large number of uncontrolled landfill sites in China. Some feasible options for improving groundwater quality are as follows: (i) Cover the landfill with an impermeable clay in order to prevent rainwater from infiltrating the waste site and reaching the landfill base. partly because the heavy metal concentrations in the sewage water and leachate are often lower than the WHO and NC standards. Han et al.. Fe and Mn close to the site. the front of the chloride plume vertically reaches a deeper depth from the ground surface. 15b) under these conditions. 15a) was therefore redistributed into each season according to the ratio of seasonal precipitation and annual precipitation in each corresponding season. Therefore. Stable isotopes (δ18O and δ2H) indicate elevation effects and/or evaporative processes prior to water reaching the saturated zone. Another factor that may affect the migration of plume beneath the landfill is the seasonal variation in water levels. The landfill itself is non-engineered. for a case where unlined and un-regulated filling occurred. leachate can easily find a path into the subsurface environment and continue to migrate in coming years. the concentrations of dissolved metals (such as Fe and Mn) in the groundwater increases. Groundwater below and around the landfill site has been contaminated by leachate. The model results indicate that the transient vertical hydraulic gradient may be the primary cause for the migration of contaminant beneath the landfill. / Journal of Geochemical Exploration 136 (2014) 24–39 Fig. These estimates indicate the lateral migration of the plume in the aquifer is limited. TDS. particularly given the high levels of domestic and agricultural groundwater use in this region. and show that surface and groundwater have similar origins of recharge. (v) Increasing the . Fe and Mn concentrations in groundwater can be identified as the main indicators and make contribution to the groundwater pollution caused by landfill leachate percolation. heavy metals do not seem to constitute a significant pollution concern at the landfill site. A two-dimensional advective–dispersive transport model was established by using MODFLOW and MT3DMS to simulate the chloride plume in the upper sand unit. and has been identified as a major threat to groundwater quality. Zn. groundwater around the Zhoukou landfill is not suitable for drinking water. and some remedial measures should be considered to improve the groundwater quality around the municipal landfill. such as the site in Zhoukou is an increasing environmental and public health concern. while As. Generally. In general. At the end of 13years. seasonal changes may be an important influence on vertical hydraulic gradients and therefore vertical flow of contaminants. (iii) Treat and purify the groundwater around the landfill for agricultural irrigation and domestic use in order to eliminate the high NO− 3 and F− concentrations. 15a). Cr and Hg are found in very low concentrations without exceedance of the WHO and NC standards. and therefore resulted in several meters of vertical migration of the contaminant plume. 15. Cl−. NH+ 4 . (iv) Close the landfill. Al and Pb locally exceed these standards. clearly demonstrated in the presence of reducing conditions and high concentrations of TDS. the use of N-fertilizers) have also extensively influenced groundwater quality in the study area. with obvious decreasing trends with increasing distance from the landfill center. sample depth. Cl−. such as recharge and water level temporal variations should be investigated further to evaluate the migration of the plume beneath the landfill. while F (probably present as a natural geological source) is more elevated in waters with high pH. accepting typical waste streams. Simulated chloride plume 13 years after the implementation of landfill in 1998 based on (a) steady sate flow model and (b) transient flow model considering seasonal variations in groundwater level. The data show the highest concentrations of As were observed in Fe-rich environments. Based on transient modeling. Se. The average annual recharge used in the steady state flow model (scenario 1) for transport simulation (Fig. NH+ 4 .38 D. (ii) Extract and recycle the leachate from the landfill base so that less leachate will enter the underlying aquifer. The seasonal dynamics of the hydraulic condition. which may result in variation in the vertical hydraulic gradient. the estimated movement of the leachate front (concentration contour line of 10 mg/L) would be ~60 m to south assuming a steady state flow. the contamination plume is still constrained in the upper aquifer. The transient flow model (scenario 2) was applied to simulate contaminant migration in the aquifer (Fig. Under the transient flow. The analysis of NO− 3 concentration distribution shows that agricultural activities (e. The simulated chloride plume was constrained in the upper sand unit in the 13 year period since the beginning of operation of the landfill (Fig. Two scenarios (steady state and transient flow model) were simulated and discussed.g. and partly because of strong attenuation by sorption and precipitation in the sedimentary aquifers. Chloride transport simulation shows that after 13 years operation of the landfill. 4. The simulated ~0. Cd.

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