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Journal of Asian Earth Sciences 70–71 (2013) 250–264

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Journal of Asian Earth Sciences

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Groundwater hydrochemical characteristics and processes along flowpaths in the North China Plain

1367-9120/$ - see front matter � 2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.jseaes.2013.03.017

⇑ Corresponding author at: School of Water Resources and Environment, ChinaUniversity of Geosciences, Beijing 100083, PR China. Tel.: +86 10 8232 1366; fax:+86 10 8232 1081.

E-mail address: [email protected] (H. Guo).

Lina Xing a,b,c, Huaming Guo a,b,⇑, Yanhong Zhan a,b

a State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083, PR Chinab School of Water Resources and Environment, China University of Geosciences, Beijing 100083, PR Chinac China Urban Construction Design & Research Institute, Beijing 100120, PR China

a r t i c l e i n f o

Article history:Received 28 October 2012Received in revised form 26 February 2013Accepted 18 March 2013Available online 28 March 2013

Keywords:AquiferGroundwater evolutionInverse modelingWater–rock interactionStable isotope

a b s t r a c t

The North China Plain is one of the biggest plains in China, where municipal, agricultural and industrialwater supplies are highly dependent on groundwater resources. It is crucial to investigate water chem-istry and hydrogeochemical processes related to hydrogeologic settings for sustainable utilization ofgroundwater resources. Two hydrochemical profiles proximately along the groundwater flow paths wereselected for hydrogeochemical study. Major components and 2H and 18O isotopes were analyzed ingroundwater samples from the profiles. The study area was divided into three zones, including strongrunoff-alluvial/pluvial fans in the piedmont area (Zone I), slow runoff-alluvial/lacustrine plain in the cen-tral area (Zone II), and discharge-alluvial/marine plain in the coastal area (Zone III). Major components ofgroundwater samples showed obvious zonation patterns from Zone I to Zone III. Total dissolved solid(TDS) concentrations gradually increased, and the hydrochemical type changed from HCO3–SO4–Ca–Mg and HCO3–Cl–Ca–Mg types to HCO3–SO4–Na–Ca, SO4–Cl–Na–Ca and SO4–Cl–Na types from Zone Ito Zone III. Abrupt increases in concentrations of Na+, Cl� and SO2�

4 in deep groundwater were observedaround the depression cones, which indicated that overexploitation resulted in water quality deteriora-tion. Calcite and dolomite precipitation occurred in Zone I of deep groundwater systems and shallowgroundwater systems. Cation exchange was believed to take place along the entire flow paths. Gypsumtended to dissolve in groundwater systems. The depletion in D and 18O isotopes in deep groundwater wasrelated to the recharge from precipitation in paleo-climate conditions in glacial or interglacial periods,indicating that renewal groundwater was very limited. Efficient strategies must be taken to preservethe valued water resources for sustainable development.

� 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Groundwater is the major resources for drinking, irrigation andindustry in arid–semiarid areas. It has been of great significance toinvestigate geochemical evolution of groundwater at basin scalesdue to its great helps in better understanding spatial and temporaldistribution of groundwater chemistry and in efficiently managinggroundwater resources for domestic, industrial and agriculturalwater supplies (Carrillo-Rivera et al., 2008; Krause et al., 2007;Ayotte et al., 2011; Hosono et al., 2009). Groundwater geochemicalevolution is controlled by both natural processes and humanimpacts. In natural systems, specific hydrogeochemical processesoccur in different hydrogeologic settings (Shen et al., 1993). In re-charge areas, dissolution of minerals (including carbonates and

silicates) dominates (Sung et al., 2012). Precipitation of secondaryminerals prevails in discharge areas (Edmunds et al., 2006). On theother hand, seawater intrusion resulting from abstraction ofgroundwater in the coastal aquifer (Vandenbohede et al., 2009;Giambastiani et al., 2007; Ghosh Bobba, 2002; Sun et al., 2010), de-cline of water levels due to shallow groundwater pumping (Gaoet al., 2007; Zhang, 2008; Yang et al., 2010), and nitrate introduc-tion to shallow groundwater due to fertilizer usage (Hamiltonand Helsel, 1995; Arnade, 1999; Cambardella et al., 1999; Krapacet al., 2002; Jalali, 2011) greatly changed geochemical processesand groundwater chemistry. In order to assess hydrogeochemicalprocesses and geochemical evolution in the complex system at ba-sin scale, many methods, including hydrogeochemical diagrams(such as Piper third-line diagrams), multivariate statistical analy-sis, water–rock interaction simulation and mineral phase equilib-rium calculations have been intensively used (Barbecot et al.,2000; Beaucaire et al., 1995; Sikdar et al., 2001; Xue et al., 2000),as well as major components, stable isotopes, trace elements andredox indicators (Plummer et al., 1990; Rademacher et al., 2001;

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L. Xing et al. / Journal of Asian Earth Sciences 70–71 (2013) 250–264 251

Edmunds et al., 2002; Condesso de Melo et al., 1999; Kretzschmarand Einsele, 1995; Adams et al., 2001).

As the largest alluvial plain in eastern Asia, the North ChinaPlain (NCP) is one of the most water scarce areas in China, withabout 450 m3 water resources per capita (Kreuzer et al., 2009).The water resource shortage has seriously impacted on economicdevelopment in the NCP (Jia and Liu, 2002; Wang et al., 2008). Inthe 1960s, many reservoirs were built in the front of the westmountain and drainage channels were built in the east plain, lead-ing to the decline of water storage in aquifers and the dry-up of riv-ers. Due to depletion of the surface water, groundwater has beenused as major water supply for agricultural, industrial and domes-tic needs since the 1970s (Zhang et al., 1992; Zhang et al., 2000).Hundreds of thousands wells were used to pump groundwaterfrom both shallow aquifers and deep aquifers to a maximum depthof 600 m. In 2003, there was 2.95 billion m3 deep groundwater ab-stracted for agricultural, industrial, and municipal purposes (Shiet al., 2010). Excessive exploitation of groundwater has causedgroundwater levels to fall at alarming rates, and led to numerousdrawdown cones with drawdowns of up to 80 m in the centersof depression cones (Chen et al., 2005b). The decline in groundwa-ter levels has greatly changed the natural groundwater flow sys-tem, including recharge, runoff and discharge conditions (Wanget al., 2008; Zhang et al., 1997, 2000; Fan, 1998; Xia et al., 2004).Therefore, many investigations have been taken to delineategroundwater flow conditions and evaluate sustainable usage ofgroundwater resources in the NCP (Zhang et al., 2009; Zhang andFei, 2009; Zhang, 2005; Zhang, 2008; Wang et al., 2009a,b; Yanget al., 2010; Xia et al., 2004; Wang et al., 2008; Shi et al., 1998;Jia and liu, 2002; Fei et al., 2009; Fan, 1998; Chen et al., 2005b).

The decline in groundwater levels may have caused severechanges of hydrochemical characteristics and geochemical pro-cesses in aquifers. Seawater intrusion was observed into coastalaquifers due to excessive exploitation (Han et al., 2011; Sunet al., 2010; Xue et al., 2000), which greatly changed naturalhydrogeochemical zones from the alluvial to the coastal plain(Liu, 1999; Zhang et al., 2000). In nine cities of the Hebei plain witha mass exploitation of groundwater, groundwater deteriorationwas found (Chen et al., 2005a). The deterioration was possiblydue to either agricultural pollution (Hu et al., 2005) or mixing ofsaline water from underlying aquifers (Chen et al., 2003; Zhang,2005) being dependent of locations. However, changes of ground-water chemistry and related geochemical processes along the flowpath are not well evaluated, which would help in better developingsuitable utilization strategies for groundwater resources in theplain impacted by intensive groundwater abstraction.

The main objectives of this study are to (1) investigate waterchemistry and isotope characteristics in typical hydrogeochemicalzones of the plain, (2) evaluate chemical evolution of groundwateralong the flow paths, and (3) assess hydrogeochemical processes indifferent hydrogeochemical zones of the plain.

2. Regional hydrogeology

2.1. Geological settings

The North China Plain (NCP) is located in the eastern part ofChina with the longitude between 112�300 and 119�300E, and thelatitude between 34�460 and 40�250N, a total area of approximately13.90 � 104 km2, and the population of about 107.8 million. Lyingbetween the west of Bohai Bay and the east of the Taihang Moun-tains, the NCP is bound to the south of the Yanshan Mountains andto the north of the Yellow River (Fig. 1).

The NCP is a large Mesozoic and Cenozoic sedimentary basinwith the Sinian bedrock as a basement, which is controlled by

the North China fault depression. The underlying geology includesthe neritic deposits of Sinian, Cambrian, Ordovician and late Car-boniferous, terrestrial-marine deposits of the Cenozoic and Perm-ian, and continental deposits of Cenozoic.

As affected by the new tectonic movements (including volcaniceruptions and seismic activities), the Yanshan Mountains and theTaihang Mountains are gradually uplifting, while the NCP is rela-tively declining since the Tertiary. Transgressions have frequentlyoccurred in the eastern coastal areas. Alluvial and fluvial sedimentsoriginating from middle and lower reaches of the Yellow River, theHaihe River, the Luanhe River and their tributaries formed sedi-mentary aquifers in the Cenozoic basin. The sediment thicknessof the Cenozoic formation is up to 1000–3500 m, with the Quater-nary deposits ranging between 200 and 600 m. The Quaternarysediments are dominated by fluvial deposits in the piedmont plain,alluvial and lacustrine deposits in the central plain, and alluvialdeposits with interbedded marine deposits in the littoral plain(Chen et al., 2003), which constitute the major aquifers for watersupply in the NCP.

2.2. Hydrogeological settings

The NCP accessible groundwater mainly occurred in the Quater-nary sediment aquifers. The regional Quaternary aquifers consist offluvial fans, alluvial fans and lacustrine deposits (Chen, 1999;Zhang et al., 2000). From the top to the bottom, sediments canbe divided into four aquifer groups according to the lithologicproperties, geological age, the distribution of aquifers and aqui-cludes, and hydrodynamic conditions (Chen et al., 2003). The depthof the first aquifer group (shallow unconfined aquifer) ranged be-tween 10 and 50 m, with coarse-grained sand in the piedmont areato fine-grained sand in the littoral plain. The second aquifer groupwas a series of shallow semi-confined aquifers with the burieddepths 120–210 m, with sandy gravel, medium to fine sand (Chen,1999). The second group was the major aquifers for groundwaterexploitation for agricultural irrigation. The third aquifer group,underlying the second aquifer group, had lower boundary between170 and 350 m (Zhang et al., 2009; Zhang, 2005; Yin and Sun,1995). This formation consists of sandy gravel in the piedmont areaand medium to fine sand in the central and littoral plain. The forthaquifer group lay below 350 m with a thickness of 50–60 m, whichconsists of cemented sandy gravel and thin layers of weatheredsand (Zhang et al., 2000). According to groundwater exploitationand aquifer distribution, groundwater can be divided into shallowgroundwater and deep groundwater (Zhang et al., 2009).Shallow groundwater mainly occurred in the first aquifergroup (shallow aquifers), while deep groundwater in the latterthree groups (deep aquifers).

Accordingly to land morphology, sediment characteristics, andgroundwater flow condition (Chen, 1999; Zhang et al., 2000; Chenet al., 2003; Zhang, 2005; Zhang and Fei, 2009), the study area canbe divided into three hydrogeochemical zones, including strongrunoff-alluvial/pluvial fans in the piedmont area (Zone I), slow run-off-alluvial/lacustrine plain in the central area (Zone II), and dis-charge-alluvial/marine plain in the coastal area (Zone III) (Fig. 2).The alluvial–pluvial area is distributed as a ribbon in shape alongthe Yanshan Mountains in the north and the Taihang Mountainsin the west. The aquifers in Zone I are mainly composed of clayeygravel and medium-coarse sand, with a high permeability. Ground-water was mainly recharged by means of lateral flow from moun-tain area and vertical infiltration from rivers and irrigation return(Wang et al., 2009a,b). Groundwater flow velocity ranged between0.013 and 0.26 m/d in Zone I, evaluated from the data by Zhang andFei (2009). The central alluvial/lacustrine plain is formed by allu-vial–lacustrine sediments, which are mainly composed of clay,silty clay, and fine-medium sand (Zhang, 2005). From the west to

Fig. 1. Hydrogeologic map of shallow aquifers (a) and deep aquifers (b) in the North China Plain.

Fig. 2. Sampling locations, water levels and profiles along which inverse geochemical modelings were performed (a) shallow groundwater; (b) deep groundwater).

252 L. Xing et al. / Journal of Asian Earth Sciences 70–71 (2013) 250–264

the east, the grain size of sediment particles decreases and the per-meability shows a decrease trend (Chen et al., 2003). Groundwaterflow velocity lay between 0.002 and 0.10 m/d in Zone II, evaluatedfrom the data by Zhang and Fei (2009). The coastal alluvial–marineplain is made of marine and alluvial sediments. It is located along

the northern and western coast of Bohai Bay. The sediments arecharacterized by fine sand, silt, sandy clay and silty clay (Fig. 1).

The study area experiences a semi-arid and semi-humid cli-mate, with the annual precipitation gradually reducing from1200 to 400 mm from the southeast to the northwest. The annual


evaporation ranges between 1000 and 2000 mm. The annual tem-perature has the range between 4 and 14 �C. The topography gen-erally inclines eastward from an altitude of about 100 m above sealevel (a.s.l.) in the west to about 1–2 m a.s.l. in the east. Land slopeis 0.5–1.8‰ in the piedmont area, 0.25–0.50‰ in the central allu-vial–pluvial area, and 0.10–0.25‰ in the coastal alluvial–marineplain (Wang et al., 2009a,b). Groundwater locally flowed fromthe top of alluvial fans, and regionally from the west to the eastor the northeast (Fig. 2). Shi et al. (1998) and Zhang et al. (2000)demonstrated that a hydraulically continuous flow system occursthrough the Quaternary aquifers in the North China Plain. Hydrau-lic gradients ranged between 1/750 and 1/2600 (Zhang et al.,2000).

3. Methods

3.1. Sampling profiles

For this study, two groundwater flow paths were selected(Fig. 2). Profile a–a0 extends from Mentougou through Langfangto Ninghe, with a total length of about 180 km. It is located inthe north of the NCP, which is along the Yongding River in theupper stream and along the New Chaobai River in the downstream. The piedmont plain of this profile is composed of YongdingRiver alluvial fans, where coarse sands are mainly present (Zone I).Due to the conjunction of the Yongding River and the New ChaobaiRiver, fine alluvial sediments occur in Zone II. The New ChaobaiRiver alluvial and the delta sediments are observed in the coastalplain (Zone III).

Profile b–b0 extends from Shijiazhuang, through Hengshui andBotou, to Tanggu, with a total length of about 380 km, which lieson the middle of the NCP. The piedmont plain of Profile b–b0 ismainly composed of Hutuo River alluvial deposits with coarse par-ticles (Zone I). The central plain is composed of alluvial sedimentsof the Yellow River and the Fuyang River characterized by finesand, silt and silty clay, and lacustrine sediments characterizedby clay, clayer silt, silt, and silty sand (Zone II). It extends fromsouth-west to north-east. The coastal plain is composed of alluvialsediments of the Yellow River, river deltas and lacustrine deposits,and marine sediments, which are mainly characterized by fine par-ticles (Zone III). Groundwater generally flows from the north-westto the south-east in Profile a–a0 and from the west/southwest tothe northeast in Profile b–b0 (Zhang and Fei, 2009).

3.2. Groundwater sampling

One hundred and thirty groundwater samples were collectedfrom wells with depths between 50 and 600 m in July 2010, amongwhich 44 samples are distributed in Profile a–a0 and 86 samples inProfile b–b0 (Fig. 2). Shallow wells had screening length around10 m, while deep wells around 50 m at the end of depths. Ground-water was sampled from each well after pumping (usually 20 min)until the flowing water showed a stabilized temperature, pH,electric conductivity (EC), and ORP. Parameters, including watertemperature, EC, pH, and ORP, were measured by using multipa-rameter portable meter (HANNA, HI 9828) in the field using anin-line flow cell to ensure the exclusion of atmospheric contamina-tion and improve measurement stability. Concentration of S2� wasmeasured using a portable spectrophotometer (HACH, DR2800)with methylene blue method. Alkalinity was determined at thetime of sampling by using a Model 16900 digital titrator (HACH)using bromocresol green–methyl red indicator. The redox potentialvalues reported in this study have not been corrected to the stan-dard hydrogen electrode (SHE), but instead can be used as relativevalues.

Water samples were collected for subsequent laboratory analy-sis. Samples for major cation and anion analysis were filteredthrough 0.45 lm membranes filters to remove suspended solidsin the field. Water samples for major cations analysis were col-lected in 125 mL polyethylene bottles, followed by addition of6 M reagent-quality HNO3 until pH < 2. Those for anions analysiswere collected in 30 mL polyethylene bottles without acidification.Those for analysis of d18O and dD were collected in 100 mL HNO3-washed polyethylene bottles with airtight caps with no headspacewithout filtration. All samples were stored at 4 �C in a refrigeratorafter sampling.

3.3. Analysis

Concentrations of major cations were determined by ICP-AES(iCAP 6300, Thermo), with the analytical precision of 0.5%. Unaci-dified aliquots were analyzed for F�, Cl�, Br�, I�, NO�3 , NO�2 , andSO2�

4 by Ion Chromatography with an instrument model ICS-1000(Dionex) within a few days after sampling. The analytical precisionof anion analysis is less than 3.0%. The chemical data was validatedusing the charge balance method, and all samples had a precisionbetter than 5%.

Oxygen and hydrogen isotope compositions were determinedusing standard methods for waters by MAT253 (Finnigan). Analyt-ical precisions of d18O and dD were ±0.1‰ and ±1‰, respectively,and expressed relative to the SMOW.

4. Results

4.1. Hydrochemical characteristics

4.1.1. Major componentsIn different hydrogeochemical zones, groundwater chemistry

was generally distinct (Fig. 3). In shallow groundwater (between10 and 100 m), sum of SO2�

4 and Cl� averagely accounted for be-tween 40% and 60% of total anions in Zone I, around 70% in ZoneII, and 90% in Zone III. Besides, sum of Ca2+ and Mg2+ averagely ac-counted for 80% of total cations in Zone I, 50% in Zone II, and 40% inZone III. Hydrochemical types from strong runoff area (Zone I) todischarge area (Zone III) changed from HCO3–Ca�Mg, throughHCO3�SO4–Na�Ca and SO4�Cl–Na�Ca, to SO4�Cl–Na.

In deep groundwater (between 100 and 600 m), sum of SO2�4

and Cl� was averagely 40% of total anions in Zone I, 80% in ZoneII. In addition, sum of Ca2+ and Mg2+ averagely accounted for 80%of total cations in Zone I, less than 40% in Zone II, and 20% ZoneIII. The dominated anions were HCO�3 in Zone I, SO2�

4 and Cl� inZone II, and HCO�3 , SO2�

4 and Cl� in Zone III. It was obvious thatCa2+ and Mg2+ were the dominated cations in Zone I, and Na+ inZone III.

Statistics of major components in shallow and deep groundwa-ters from different zones are given in Tables 1 and 2, respectively.Shallow groundwater showed increasing trends in concentrationsof Na+ and Cl�, and decreasing trends in concentrations of Ca2+,HCO�3 , and SO2�

4 from zone I to zone III (Table 1). Concentrationsof K+ and Mg2+ were the lowest in shallow groundwaters of ZoneIII. In deep groundwater, concentrations of Ca2+ and Mg2+ graduallydecreased from zone I, through zone II, to zone III, with the highestconcentrations of 137 and 42.6 mg/L in Zone I, respectively (Ta-ble 2). In contrast, concentrations of Na+, Cl�, SO2�

4 and TDS gener-ally increased from Zone I to Zone III. Median values of Na+ were28.0, 197, and 327 mg/L for Zones I, II, and III of Profile b–b0, respec-tively. In comparison with Zone II, concentration of K+ was higherin Zone I and Zone III, ranging between 0.5 and 4.6 mg/L. Thehighest SO2�

4 concentration (449 mg/L) was observed in Zone IIIof Profile b–b0 (Table 2).

Fig. 3. Piper diagram of shallow groundwater (a) and deep groundwater (b) in Profile a–a0 , and shallow groundwater (c) and deep groundwater (d) in Profile b–b0 in the NorthChina Plain.

Table 1Statistics of major components of shallow groundwater samples in different zones (mg/L).

Profile K+ Ca2+ Na+ Mg2+ HCO�3 SO2�4

Cl� TDS

a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0

Zone I Min 1.0 0.9 47.0 39.8 33.6 19.3 35.2 23.6 250 190 51.3 42.6 37.9 21.5 468 269Med 3.6 2.5 137 139 104 44.7 61.4 34.9 504 304 159 131 154 74.3 961 674Max 16.3 4.3 178 243 227 99.9 103 69.2 744 521 239 219 206 293 1260 1150

Zone II Min 3.5 0.8 27.5 6.7 68.6 67.1 32.1 4.2 536 86.9 5.4 81.8 36.0 69.3 658 549Med 3.9 2.2 71.9 63.2 124 203 41.7 48.8 595 386 23.0 295 103 141 675 972Max 4.3 3.4 116 125 179 335 51.3 82.5 655 543 40.6 686 169 312 692 1740

Zone III Min 0.5 0.9 6.8 6.5 91.9 201 1.9 3.7 106 215 5.3 56.7 27.0 50.3 270 578Med 1.3 1.1 12.3 7.0 103 275 4.5 4.4 210 356 19.5 67.1 63.0 188 296 688Max 3.2 2.0 16.1 28.7 119 452 6.5 29.1 223 559 27.7 293 103 443 381 1430


Depth dependence of chemical components was different be-tween Profile a–a0 and Profile b–b0 (S1 in Supporting materials).Concentrations of Ca2+, TDS, HCO�3 , and Cl� generally showed de-crease trends with depth in Profile a–a0. In contrast, Na+, TDS,

and Cl� concentrations had increasing trend with depth in Profileb–b0. The different behavior between two profiles may relate togroundwater exploitation practice. It showed overexploitationalong the Profile b–b0 (Chen et al., 2002; Zhang et al., 2009). On

Table 2Statistics of major components of deep groundwater samples in different zones (mg/L).

Profile K+ Ca2+ Na+ Mg2+ HCO�3 SO2�4

Cl� TDS

a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0 a–a0 b–b0

Zone I Min 0.6 1.0 35.1 20.8 26.1 10.3 10.8 7.6 185 156 36.4 20.8 23.5 9.8 324 251Med 2.4 2.3 62.5 62.3 60.2 28.0 33.3 19.3 291 209 63.8 64.1 53.5 22.3 455 287Max 4.6 3.2 104 137 123 67.6 42.6 37.3 440 291 148 149 131 139 703 665

Zone II Min 0.8 0.5 10.8 4.8 118 69.1 2.3 2.1 163 3.0 15.6 48.1 48.2 11.6 330 309Med 1.1 1.1 12.8 13.3 142 197 6.4 8.7 276 201 38.1 148 57.5 119 420 589Max 1.1 4.9 14.2 49.0 216 270 9.3 32.6 453 383 61.4 308 71.0 316 539 982

Zone III Min 0.5 0.6 4.2 2.3 80.9 154 0.8 0.5 85.5 168 8.2 31.4 20.6 35.7 241 376Med 1.2 1.5 9.6 7.6 112 327 3.0 5.4 211 296 20.4 164 41.0 194 342 917Max 4.1 3.7 31.1 25.5 227 585 26.1 21.2 371 380 94.5 449 194 523 709 1720


the other hand, high NO�3 concentration in shallow groundwater ofboth profiles may be associated with pollution from agriculturalactivities. Shallow groundwater had high NO�3 concentrations, upto 230 mg/L. However, NO�3 concentrations of deep groundwaterwere mostly less than 25 mg/L at depths >200 m.

4.1.2. Hydrogen and oxygen isotopesPlot of dD and d18O is shown in Fig. 4. All data were close to the

LMWL (dD = 7.02341 d18O + 1.72339, R2 = 0.95) (Zhang et al., 2000),and shifted to the right of the global meteoric water line (GMWL)(Claassen, 1985; Thomas et al., 1996). It was suggested thatgroundwaters were mainly derived from local meteoric water.Most of samples were enriched in 18O isotope and located to theright of the LMWL, which indicated that the meteoric water expe-rienced different extents of evaporation before recharge (Allen,2004).

The dD values of Zone I water samples ranged from �82‰ to�43‰ (median �61‰), whereas the d18O values ranged from�10.1‰ to �5.0‰ (median �7.9‰). dD and d18O of groundwatersfrom Zone I were mostly plotted near LMWL, suggesting thatgroundwater was directly recharged by precipitation with weakevaporation. The values of dD and d18O from Zone II were both low-er than those in Zone I. In Zone II, the dD values ranged from �95‰

to �58‰ (median �80‰), and d18O values from �12.1‰ to �7.6‰

(median �10.5‰). The values of dD and d18O from Zone III were a

Fig. 4. Plots of dD and d18O in groundwaters of the North China Plain (legend of thelines: GMWL line indicates global meteoric water line; LMWL line indicates NorthChina Plain’s meteoric water line; YDRWL line indicates the Yong Ding River Waterline; legend of the sample symbols the same as in Fig. 3).

little higher than those in Zone II, and lower than those in Zone I,with the median values of �73‰ and �9.0‰, respectively.

There were big differences in hydrogen and oxygen isotope val-ues between shallow and deep groundwater. Generally, deepgroundwaters were depleted in d18O and dD (with medians of�73‰ and �9.2‰, respectively), compared to shallow groundwa-ters (with medians of �59‰ and �7.7‰, respectively). Deepgroundwater samples, being more negative and plotted signifi-cantly to the right of the global meteoric water line (GMWL),showed a paleorecharge effect (Clark and Fritz, 1997).

Especially, the d18O and dD isotope signatures of groundwatersfrom Zones II and III of deep aquifers may be related to precipita-tion in paleo-climate conditions. The precipitation of the last ice-age had lower dD and d18O values due to lower temperature(Varsányi and Kovács, 2009; Chen et al., 2002). Both Chen et al.(2003) and Kreuzer et al. (2009) suggested that Pleistocenegroundwater samples presumably recharged during last glacialperiod had a range from �9.4‰ to �11.7‰ for d18O, and �76‰

to �85‰ for dD in the NCP. Recharge of these waters was thoughtto have occurred at the end of the Pleistocene, hardly being af-fected by evaporation (Kreuzer et al., 2009). Therefore, the hydro-gen and oxygen isotope signatures in deep groundwater mayreflect the groundwater recharged from precipitation in glacial orinterglacial periods.

4.2. Groundwater hydrochemistry along the flow paths

Trends of groundwater chemistry along the flow paths providedimportant clues to the hydrogeochemical processes in the basin-scale study (Rosen and Jones, 1998). Variations in isotopic and ma-jor components along the flow paths are shown in Fig. 5.

From Zone I through Zone II to Zone III, change trends in dD andd18O of shallow groundwaters were similar to deep groundwaters(Figs. 5a–d). In the Profile a–a0, both shallow groundwater and deepgroundwater showed decreasing trends in dD and d18O values inZones I and II, and relatively stable in Zone III. However, for theProfile b–b0, both dD and d18O values declined firstly from Zone Ito Zone II, and then increased in Zone III with the distance awayfrom the recharge area for both shallow groundwaters and deepgroundwaters. The depletion in both D and 18O of deep groundwa-ter from Zone II possibly implied that groundwater was principallymaintained by palaeowater that originated under a cold environ-ment during late Pleistocene and early Holocene (He et al., 2012).The enrichment of D and 18O in Zone III of the Profile b–b0 wouldresult from the impact of marine waters (Clark and Fritz, 1997).

Decreasing trends in Ca2+ concentrations were observed in ZoneI along the flow paths (Fig. 5e–f). In Profile a–a0, shallow groundwa-ter Ca2+ decreased from 180 mg/L in Zone I to around 20 mg/L inZone II, and deep groundwater Ca2+ declined from 104 mg/L inZone I to 7.0 mg/L in Zone II. However, Na+ concentration keptrelatively stable in both Zones I and II. In Profile b–b0, Na+

Fig. 5. Variation of dD and d18O and major components along the flow paths (a, c, e, g, and i from profile a–a0; b, d, f, h, and j from profile b–b0; d shallow groundwatersamples; N deep groundwater samples).


concentration increased from around 50 mg/L to around 270 mg/Lfor shallow groundwater and from around 30 mg/L to around300 mg/L for deep groundwater from Zone I to Zone III (Fig. 5g–h).Trends in Ca2+ and Na+ variations along the flow paths may giverise to ionic exchange between water Ca2+ and Na+ in the solids(Hem, 1992; Belkhiri et al., 2010; Ako et al., 2012).

Variation trends in HCO�3 concentration at Profile a-a0 and Pro-file b–b0 were complex, which increased in Zone I and declined inZones II and III of Profile a–a0, and kept relatively stable in Zone Iand increased from Zone II to Zone III of Profile b–b0 (S2a–b in Sup-porting materials). The variations may attribute to dissolution andprecipitation of carbonates, rainwater recharge, and seawater im-pacts. Concentrations of Cl� had the same trends as SO2�

4 from ZoneI to Zone III (Fig. 5g–h and S2c–d in Supporting materials). For Pro-file a–a0, both SO2�

4 and Cl� decreased from Zone I to Zone II, andkept relatively constant in Zones II and III. In Profile b–b0, SO2�

4

and Cl� concentrations generally showed increasing trends fromZone I to Zone III for both shallow groundwater and deep ground-water. However, SO2�

4 and Cl� reached the highest near Hengshuicity and Tianjin city in deep groundwater from Zone II and ZoneIII, respectively. The possible reason was the vertical recharge(upconing) of saline groundwaters from lower aquifers in thegroundwater depression cones due to heavy exploitation in thosecities (Han et al., 2011). It was reported that deep groundwater le-vel declined to 75 m below sea level (b.s.l.) at the rate of 3 m/a in2009 in Hengshui city, and 95 m b.s.l. in Tianjin city (Fei et al.,2009). Chen et al. (2003) observed that about 10–20% saline waterwas mixed with fresh water in depression cone areas. It impliedthat overexploitation not only greatly changed water levels, butalso resulted in groundwater deterioration.

Nitrate showed decreasing trends from Zone I to Zone II andkept steady through Zone III in shallow groundwater and deep

Fig. 5. (continued)


groundwater of both profiles (S2e–f in Supporting materials).Among 16 samples from shallow groundwater in Zone I of Profilea–a0, nine samples had NO�3 concentrations greater than 50 mg/L,which is the recommended drinking water quality standard forNO�3 (WHO, 2011). Besides, 52% of samples from shallow ground-water had concentrations greater than 50 mg/L in Zone I of Profileb–b0. All of groundwaters in Zones II and III showed low NO�3 con-centrations (<50 mg/L). The higher NO�3 concentration in shallowgroundwaters than deep ones from Zone I of both profiles maybe related to anthropogenic pollution from agricultural and indus-trial activities due to high permeability of alluvial fans (Hu et al.,2005).

Fig. 6. Gibbs diagram of groundwater samples in the North China Plain (the grayshaded area was proposed by Gibbs to reflect rock weathering dominance (RWD),TDS values below the shaded area were proposed to atmospheric precipitationdominance (APD), and TDS values above the shaded area are dominated byevaporation–crystallization dominance (ECD). Legend of the sample symbols thesame as in Fig. 3).

5. Discussion

5.1. Hydrogeochemical processes

5.1.1. Hydrolysis processThe soluble ions in natural waters mainly come from the rock

and soil weathering (Lasaga et al., 1994), anthropogenic input,and partly from the atmosphere input. Gibbs diagram could beused to analyze the genesis mechanisms of water chemistry(Wanty et al., 2009; Mamatha and Sudhakar, 2010; Feth and Gibbs,1971; Kilham, 1990; Négrel, 1999). According to Gibbs (1970), riv-ers may have an assemblage of dissolved loads that reflect domi-nant effects of precipitation, rock weathering, or evaporation indry regions. The ratios of Na+/(Na+ + Ca2+) were mostly less than0.5 in deep groundwater from Zone I, with low TDS values(Fig. 6). This suggested that rock weathering was the dominantmechanism (Wang et al., 2010). In shallow groundwater, about2/3 of samples had the ratios less than 0.5 and high TDS, which

suggested that rock weathering and evaporation–crystallizationwere the mechanisms controlling the groundwater chemistry in

Fig. 7. Stability field diagrams for the Na+–H+–SiO2 (a) and Ca2+–H+–SiO2 (b) systems in groundwaters from the North China Plain (Abbreviations: Qtz. Sat. – Quartz saturationline; Am. SiO2 Sat. – amorphous SiO2 saturation line. Legend of the sample symbols the same as in Fig. 3).


shallow groundwater. Samples from Zones II and III were mainlylocated on the upper right of the diagram, with Na+/(Na+ + Ca2+) ra-tio greater than 0.5 and TDS between 241 and 5910 mg/L, whichshowed that the groundwater chemistry was not only controlledby rock weathering and/or atmospheric precipitation, but also bymixing of saline water or evaporation.

Mineral stability diagrams were usually used to assess thedegree of fluid–rock equilibrium. Although the diagrams wereoriginally designed for hydrothermal fluids (Giggenbach, 1988), alot of work on ambient groundwaters has shown applicability tolow temperature systems (Grimaud et al., 1990; Beaucaire et al.,1999). In order to study the equilibrium of groundwater with sili-cate, the Na+–H+–SiO2 and Ca2+–H+–SiO2 mineral balance diagramswere employed (Fig. 7), and both showed that all samples lay in thekaolinite stability field. It was suggested that primary silicate min-erals, such as albite, should be dissolved and weathered to kaolin-ite in the groundwater systems, as shown in Eq. (1) (Herczeg, 2001;Wang et al., 2009a,b). This was in good agreement with calculationof saturation indices (SI) for selected minerals by the hydrogeo-chemical code PHREEQC (Parkhurst and Appelo, 1999) usinggroundwater chemical data, showing that all groundwaters wereunder-saturated with respect to albite (data now shown).

4NaAlSi3O8ðAlbiteÞ

þ4CO2 þ 22H2O ¼ Al4Si4O10ðOHÞ8ðKaoliniteÞ

þ4Naþ

þ 8H4SiO4 þ 4HCO�3 ð1Þ

Fig. 8. Variation of Cl� concentration with Br� concentration (a) and Cl/Br ratio (b) in grLegend of the sample symbols the same as in Fig. 3).

In addition, the saturation indices for quartz were mostly great-er than zero with SIquartz between 0.2 and 0.7, except three samplesfrom Zone III of Profile a–a0 (data not shown). It indicated thatgroundwater samples were over-saturated with respect to quartz.The weathering of quartz may be limited in the groundwater sys-tems of the NCP.

5.1.2. Evaporation processRatios of Cl� to Br� in a predictable manner are important

invaluable tracers for geochemical processes, which can be usedto distinguish evaporation–crystallization from other processes,such as halite dissolution (Cartwright et al., 2006). It was foundthat Br� concentration was positively correlated with Cl� concen-tration (Fig. 8a), indicating that evaporation generally occurred inthe groundwater systems. Bromide in Zone III had concentrationsaround 0.006 mmol/L, except for four samples with high concen-trations around 0.014 mmol/L.

Seawater generally has a constant molar Cl/Br about 650 (Drev-er, 1997; Davis et al., 1998, 2001). Coastal rainfall generally hassimilar Cl/Br ratios, but inland rainfall may have different Cl/Br ra-tios in different locations. Inland basins, especially in arid orsemi-arid areas, have lower Cl/Br ratios due to the tendency forCl� to be removed by deposition of marine aerosols in coastal areas(Edmunds, 2001; Cartwright et al., 2006). However, Cl/Br ratios ofhalite are commonly 104–105, because halite could prevent morebromine from entering its mineral lattice (Kloppmann et al.,2001; Cartwright et al., 2006).

oundwaters (the line of linear regression in (a) is for shallow groundwater samples.


The range of Cl/Br ratios in groundwaters was between 100 and2500. Relatively lower ratios were observed in groundwaters fromZones I and II (<1700), in comparison with those in Zone III(Fig. 8b). Since all samples were unsaturated with respect to halite,with SIHalite between �8.26 and �3.32, dissolution of halite led tothe rapid increase in Cl/Br ratio as well as Cl� concentration(Fig. 8b). In Fig. 8b, deep and few shallow groundwater samplesin Zone I were plotted near the equilibrium molar concentrationline, indicating that dissolution of halite (NaCl) occurred. It wassuggested that groundwaters in Zone I with lower Cl/Br ratios werestrongly affected by rainfall and weakly affected by evaporation.

Shallow groundwaters in Zones II and III had generally constantCl/Br ratios and high Cl� concentration (Fig. 8b). Evaporation pro-cess did not change the Cl/Br ratios until the halite were saturated,although residual water were relatively enriched in Br� and Cl�.Therefore, evaporation indicatively was the dominant factor affect-ing groundwater chemistry of shallow groundwater from Zones IIand III.

5.1.3. Ion exchange processAlthough deep groundwater samples in Zones II and III were

mostly located in the upper right of Gibbs diagram (Fig. 6), theydid not fall in the banana-shaped area. These deep groundwatershad the ratios of Na/(Na + Ca) greater than 0.5, and TDS between241 and 2120 mg/L. The ratios of Na/(Na + Ca) increased from ZoneII to Zone III, while total dissolved solid (TDS) was identical in Pro-file a–a0 and increased in Profile b–b0. It implies that cation ex-change may be an important process for the dominance of Na+ inthe cations in deep groundwaters of Zones II and III possibly dueto the abundance of adsorbed Na+ in aquifer sediments and/orthe increase in groundwater TDS in the Profile b–b0, instead ofevaporation. The increase in Na/(Na + Ca) would also be explainedby ion exchange reaction, as in groundwater of Chihuahua Desert(Texas USA) observed by Fisher and Mullican (1997), and in thePampean loessic aquifers by Cirelli and Miretzky (2004).

Ion exchange between Ca2+, Mg2+ and Na+ in groundwater sys-tems is very important for groundwater hydrochemical evolution.In both shallow groundwater and deep groundwater, Na+ concen-tration and [Na]/[Ca], [Na]/[Mg] molar ratios gradually increasedfrom Zone I, through Zone II, to zone III (Table 3). Average molarratios of [Na]/[Ca] and [Na]/[Mg] increased from 1.2 and 1.5 inZone I to 31.0 and 36.5 in Zone III of shallow groundwater, respec-tively (Table 3). These increases were expected to result from ionexchange between adsorbed Na+ and Ca2+ and Mg2+ from solution(Jiang, 2009).

The aquifer sediments were characterized by medium sand andfine-mid sand in Zone I, and gradually finer in Zones II and III withan increase in clay mineral contents and adsorbed Na+. Therefore,Ca2+ and Mg2+ in the waters would have exchanged with Na+ pre-viously absorbed on the surface of clay minerals in the aquifer ma-trix of Zones II and III due to the increase in groundwater TDS asshown in Eq. (2) (Guo and Wang, 2004). This reaction would de-

Table 3Average molar ratios of [Na]/[Ca] and [Na]/[Mg] in shallow and deep groundwatersfrom different zones.

[Na]/[Ca] [Na]/[Mg]

Zone I Shallow groundwater 1.2 1.5Deep groundwater 1.5 2.2

Zone II Shallow groundwater 13.6 11.7Deep groundwater 29.8 35.4

Zone III Shallow groundwater 31.0 36.5Deep groundwater 50.6 73.2

crease concentrations of Ca2+ and Mg2+ and increase Na+ concen-tration in groundwater (Hidalgo and Cruz-Sanjulian, 2001).

Na2 ðClayÞ þ ðCa2þ þMg2þÞ ðGroundwaterÞ

$ ðCa2þ þMg2þÞ ðClayÞ þ 2NaþðGroundwaterÞ ð2Þ

The molar ratio of Na+ to Cl� can be used to reflect the ion ex-change degree (Li, 2010). Most of groundwater samples had Na+/Cl� ratios greater than 1 (Fig. 9a). In addition, Na+/Cl� ratio showeda decreasing trend with an increase in Cl� concentration. The rea-son for the weak ion exchange in high Cl� groundwater was thatNa+ concentration increased due to evaporation and became highenough to balance the adsorbed Na+ for ion exchanged cations,although the increase in TDS would be driving force for cation ex-change. It indicated that evaporation would gradually suppress ionexchange between aqueous Ca2+ and adsorbed Na+. Besides, Mg2+

in groundwaters could be involved into the ion exchange, whichwas supported by meq ratio of Na+ to (Na+ + Ca2+ + Mg2+). The ratioincreased from Zone I to Zone III, and exhibited higher in deepgroundwaters than in shallow groundwaters (Fig. 9b).

5.1.4. Redox processesAlthough pH was higher in deep groundwaters than shallow

groundwaters, it showed increasing trends from Zone I to ZoneIII (S3a in Supporting materials). For deep groundwaters, pH ran-ged between 7.5 and 8.6 in Zone III, while between 6.7 and 8.2 inZone I, and between 6.8 and 8.3 Zone II.

Generally, ORP values of deep groundwaters were lower thanshallow groundwaters in each hydrogeochemical zone (S3a in Sup-porting materials). In Zone I, the values ranged from 0 to 250 mV inshallow groundwaters, while from �30 to 130 mV in deep ground-waters. In both shallow groundwaters and deep groundwaters,ORP values were high in Zone I and showed decreasing trends fromZone I to Zone III. For deep groundwaters, the values ranged be-tween �30 and 130 mV, between �220 and 150 mV, and between�250 and 100 mV in Zone I, Zone II and Zone III, respectively. Itshowed that groundwaters in Zone I occurred in oxic conditions,while in Zones II and III in weakly reducing conditions.

In Zone I, SO2�4 concentration generally showed an increase

trend when HCO�3 concentration increased in shallow groundwater(S3b in Supporting materials). It suggested that oxidation of sulfideand/or dissolution of carbonate should occur in shallow groundwa-ters. However, in Zone II or Zone III, SO2�

4 concentration generallydecreased with increasing HCO�3 concentration. Since saturationindex of gypsum was less than 0 (data not shown), the loss ofSO2�

4 could not be explained by gypsum precipitation. It impliedthat SO2�

4 reduction would take place in both Zones II and III. Thisspeculation was evidenced by the presence of S2� in groundwaters.Groundwaters from Zone I contained S2� concentration less than2 lg/L, while from Zones II and III mostly greater than 6 lg/L.Reduction of SO2�

4 produced HCO�3 and concurrently increasedpH, as shown in Eq. (3). Relatively higher pH and HCO�3 concentra-tion in Zones II and III of Profile b–b0 also supported the process ofSO2�

4 reduction. Since bacterial sulfate reduction would lead to theenriched d34S values of SO2�

4 (Stüben et al., 2003; Guo et al., 2011)and the depleted d13C values of DIC (Clark and Fritz, 1997; deMontety et al., 2008), further investigations of 34SSO4 and 13CTDIC

will be carried out to confirm this possibility.

SO�24 þ 2Cþ 2H2O ¼ H2Sþ 2HCO�3 ð3Þ

5.2. Evidences from Inverse modeling

Inverse modeling is to determine sets of mole transfers ofphases that account for changes in water chemistry between aninitial water composition and a final water composition (Parkhurst

Fig. 9. Variation of Cl� concentration with Na+/Cl� meq ratio (a) and Na+/(Na+ + Ca2++Mg2+) meq ratio (b) in groundwaters of the North China Plain (legend of the samplesymbols the same as in Fig. 3).

Table 4Possible mineral phases and their dissolution reactions.

Mineral phases Dissolution reactions

Calcite CaCO3 ¼ Ca2þ þ CO2�3

Dolomite CaMgðCO3Þ2 ¼ Ca2þ þMg2þ þ 2CO2�3

Albite NaAlSi3O8 þ 8H2O ¼ Naþ þ AlðOHÞ�4 þ 3H4SiO4

Fluorite CaF2 = Ca2+ + 2F�

Halite NaCl = Na+ + Cl�

Gypsum CaSO4 � 2H2O ¼ Ca2þ þ SO2�4 þ 2H2O

Sylvite KCl = K+ + Cl�

CO2 CO2 þ H2O ¼ H2CO03

Cation exchange Ca M 2Na, Ca M Mg, Mg M 2Na


and Appelo, 1999). Helgeson (1968) used inverse modeling to sim-ulate the processes of water–rock interaction and the mass transferbased on groundwater chemical data. Accordingly, geochemicalprocesses along the groundwater flow paths can be quantitativelydescribed, in case that groundwater chemistry and possible min-eral phases are known (Plummer and Back, 1980). The mineralphases could be gases, minerals and/or ions involved in cation ex-change reaction (Parkhurst and Appelo, 1999). The inverse modelswere formulated so that gypsum, dolomite, and CO2 were con-strained to dissolve until they reached saturation, and calcite wasset to precipitate once it reached saturation. The hydrogeochemicalcode PHREEQC was employed to perform inverse modeling in thisstudy.

Water samples were selected in each profile to perform inversemodeling for simulation. In Profile a–a0, samples 1S-1–1S-8 and1D-1–1D-8 are shallow and deep groundwater samples, respec-tively. Samples 2S-1–2S-10 and 2D-1–2D-12 are shallow and deepgroundwater samples from Profile b–b0, respectively (Fig. 2). Thesesamples were representative for variation trends in each zone ofeach profile.

5.2.1. Possible mineral phasesThe determination of possible mineral phases is very important

for inverse modeling, which is based on mineral compositions ofaquifer sediments, groundwater chemical components and theoccurrence condition of aquifers (Güler and Thyne, 2004). The min-erals contained in aquifer sediments are the first priority of thepossible mineral phases. In both shallow aquifers and deep aqui-fers, sediments are mainly composed of quartz, calcite, dolomite,albite, fluorite, halite, gypsum, and sylvite (Chen and Ni, 1987).The shallow groundwater system is in open state, CO2 and O2 areregarded as possible phases as well. In addition, the cation ex-changes between Ca2+ and Na+, Mg2+ and Na+ are very importantduring groundwater chemical evolution processes (Shen et al.,1993). Clay minerals were considered as adsorbents for cation ex-changes. Possible mineral phases and their dissolution reactionsare shown in Table 4.

5.2.2. Shallow groundwater systemResults of inverse modeling in shallow groundwaters of Profile

a–a0 are shown in Table 5. Simulation results showed that thehydrogeochemical processes were different in different zonations.In Zone I, shallow groundwater system experienced precipitationsof dolomite and gypsum, and dissolutions of halite, fluorite, andCO2, cation exchange (between K+ and Na+ in sediments and Ca2+

in water), and weak evaporation (Table 5). In Zone II, it experiencedprecipitations of calcite, dolomite, fluorite, and sylvite, CO2 release,

dissolutions of halite and gypsum, cation exchange, and strongevaporation. In Zone III, precipitations of calcite and dolomite, dis-solutions of halite and albite, and cation exchange were domi-nated. Sulfate reduction was stronger in Zone III than Zone II.

Shallow groundwaters of Zone I in Profile b–b0 experienced pre-cipitations of calcite and dolomite, halite dissolution, cation ex-change, and evaporation (Table 6). The simulation results showedthat, in addition to calcite and dolomite precipitations, CO2 release,halite and gypsum dissolutions, cation exchange, sulfate reduction,and evaporation occurred in Zone II. Hydrogeochemical processesin Zone III were the same as Zone II (Table 6).

In summary, cation exchange, evaporation, and halite dissolu-tion generally occurred in all zones of shallow groundwater sys-tems. Based on inverse modeling, Belkhiri et al. (2012) observedthat the dissolution of carbonate and evaporite minerals occurredin the recharge area of an alluvial aquifer. Calcite and dolomiteprecipitations were expected to take place in Zone II. Althoughevaporation was normally observed in shallow groundwaters ofarid–semiarid areas (Edmunds et al., 2006; Zhu et al., 2007; Heet al., 2012), evaporation was much stronger in Zones II and III thanthat in Zone I since buried depths of groundwater table in Zones IIand III were shallower. However, sulfate reduction was mainlypresented in Zones II and III.

5.2.3. Deep groundwater systemsFor Profile a–a0, precipitations of calcite and dolomite, dissolu-

tions of halite and gypsum, cation exchange and weak sulfatereduction occurred in deep groundwaters of Zone I (Table 7). Incomparison with shallow groundwater, CO2 from deep groundwa-ter in Zone II turned to be dissolved instead of being degassing. InZone III, groundwater experienced precipitations of calcite and

Table 5Results of inverse modelings of shallow groundwaters along Profile a–a0 (in mmol/L).

Mole transfers Zone I Zone II Zone III

1S-1 ? 1S-2 1S-2 ? 1S-3 1S-4 ? 1S-5 1S-6 ? 1S-7 1S-7 ? 1S-8

Dolomite – �0.04 �11.8 – �0.03Calcite – – �4.0 �0.07 �0.09Gypsum �0.13 �0.03 0.02 0.05 0.10Halite 1.00 1.0 3.3 2.2 0.16Fluorite 0.01 �0.46 �0.03 �0.003Sylvite 0.09 �0.08 �12.5 �0.06 �0.008H2O(g) �1110 �1180 �2620 �3050 –CO2(g) – 2.7 �2.6 �0.22 �0.84NaX 0.31 2.1 3.5 0.27 1.3CaX2 �0.82 �1.6 �17.8 – �0.78MgX2 0.67 0.57 – 0.14 –Albite – – – 0.30 –Sulfate reduction – – 5.4 7.9 11.2

‘‘–’’ data not available. Thermodynamic database used: phreeqc.dat. Positive values indicate dissolution (mass entering water), and negative values indicate precipitation(mass leaving water).

Table 6Results of inverse modelings of shallow groundwaters along Profile b–b0 (in mmol/L).


2S-1 ? 2S-2 2S-2 ? 2S-3 2S-4 ? 2S-5 2S-5 ? 2S-6 2S-6 ? 2S-7 2S-8 ? 2S-9 2S-9 ? 2S-10

Dolomite �0.22 – �57.8 – – – �18.8Calcite – �2.8 – – �2.2 – –Halite 3.9 2.5 2.0 7.6 3.9 12.4 �2.3Gypsum �0.01 – 0.03 0.30 0.05 0.05 0.35Fluorite 0.01 0.001 0.01 0.01 0.01 0.15 �0.09Sylvite �0.03 0.02 0.02 0.04 �0.22 0.05 0.01H2O(g) – �3900 – �4210 �1790 – –CO2(g) – – – �0.48 – �5.8 �7.9NaX 3.5 5.6 1.8 – 6.0 8.3 7.3CaX2 �1.8 �2.4 �60.4 �1.2 �33.5 �5.4 �3.6MgX2 – �0.56 59.5 1.2 – 1.2 –Albite – – – – 3.2 – –Sulfate reduction – – 2.5 – 9.6 10.0 17.5


Table 7Results of inverse modelings of deep groundwaters along Profile a–a0 (in mmol/L).


1D-1 ? 1D-2 1D-2 ? 1D-3 1D-4 ? 1D-5 1D-6 ? 1D-7 1D-7 ? 1D-8

Dolomite �0.04 – �0.30 �0.23 –Calcite �1.0 – �1.9 – �1.4Gypsum – 0.58 0.08 0.06 0.10Halite 2.4 0.65 0.69 �0.89 0.16Fluorite �0.01 0.02 �0.02 �0.09 �0.05Sylvite – – �0.01 0.04 0.02CO2(g) �1.0 3.2 0.61 �1.0 �1.7NaX – 1.7 – – –CaX2 – �1.7 �0.29 – –MgX2 – 0.80 0.29 –Albite – – – 1.2 1.4Sulfate reduction – 0.59 1.6 4.4 18.5



dolomite, CO2 release, dissolutions of gypsum and albite, andstrong sulfate reduction.

Deep groundwaters of Zone I in Profile b–b0 experienced precip-itations of dolomite and gypsum, dissolutions of fluorite, halite andalbite, weak cation exchange and sulfate reduction (Table 8). Be-tween 2D-5 and 2D-6 in the direction from west to east (Zone II),precipitations of calcite, dolomite, and sylvite, CO2 release, anddissolutions of gypsum, halite, and fluorite, and sulfate reduction

occurred. Between 2D-7 and 2D-8 in the direction from southeastto northeast (Zone II), groundwaters showed stronger sulfatereduction than between 2D-5 and 2D-6. Groundwaters in Zone IIIexperienced gypsum and halite dissolutions, cation exchange,and sulfate reduction.

The dissolutions of gypsum, halite and fluorite generally oc-curred in deep groundwater systems, which were also observedin groundwaters from Taiyuan basin, China (Guo et al., 2007) and

Table 8Results of inverse modelings of deep groundwaters along Profile b-b0 (in mmol/L).


2D-1 ? 2D-2 2D-2 ? 2D-3 2D-3 ? 2D-4 2D-5 ? 2D-6 2D-7 ? 2D-8 2D-9 ? 2D-10 2D-10 ? 2D-11 2D-11 ? 2D-12

Dolomite �0.89 – �0.44 �0.89 �0.03 – – –Calcite – – – �0.64 �0.74 – – –Gypsum �1.9 �0.32 – 0.68 0.63 3.4 – 1.8Halite 1.6 0.30 0.65 2.7 0.84 13.7 2.7 6.6Fluorite 0.01 0.01 0.02 0.0002 0.03 0.05 �0.04Sylvite 0.02 �0.01 �0.02 �0.12 �0.02 0.09 �0.05 –CO2(g) 4.1 2.3 �0.88 �3.8 – �2.5 �0.94 0.63NaX – – 0.55 – – 7.1 – 9.4CaX2 – �0.19 – – – �4.0 �0.28 �4.0MgX2 – 0.19 – – – 0.46 0.28 �0.68Albite 2.5 0.60 – – 1.8 – 0.43 �10.0Sulfate reduction 1.3 – 4.3 4.2 14.3 17.5 2.6 9.3



from the Tivali Plain of Italy (Carucci et al., 2012). Cation exchangewas universally found as well. This process was also used to ex-plain the simultaneous increase in Na+ concentration and de-creases in Ca2+ and Mg2+ concentrations in groundwaters (Hanet al., 2011; Chae et al., 2006).

In summary, calcite and dolomite precipitations occurred indeep groundwater systems and shallow groundwater systems. Cat-ion exchange was believed to take place along the whole flowpaths. Gypsum and halite tended to be dissolved in groundwatersof Zones II and III. In addition, sulfate reduction was expected tooccur in Zones I, II and III of deep groundwaters. Evaporation wasonly found in shallow groundwater systems. Although chemicalprocesses along Profile a–a0 were identical to those along Profileb–b0, groundwater mixing between deep groundwater and salinewater would occur in depression cones of Profile b–b0 which wasevidenced from chemical and isotope variations.

6. Conclusions

Groundwater chemistry showed evident difference from Zone I,through Zone II, to Zone III. Water type from Zone I through Zone II,to Zone III changed from HCO3–Ca�Mg and HCO3�SO4–Ca�Mg,through HCO3�SO4–Ca�Na and SO4�Cl–Na�Ca, to SO4�Cl–Na, andCl–Na in shallow groundwaters. In deep groundwaters, water typechanged from HCO3–Ca�Mg, HCO3�SO4–Ca�Mg, through SO4�Cl–Na�Ca, SO4–Na, to SO4�Cl–Na and HCO3�SO4–Na. Shallow ground-water had higher NO�3 concentrations than shallow groundwater,showing the possibility of groundwater contamination by agricul-tural and industrial activities. Along the groundwater flow paths,Na+, and Cl� showed increasing trends from zone I, through zoneII, to zone III in shallow groundwater. In deep groundwater, Ca2+

and Mg2+ decreased, Na+, SO2�4 , Cl� and TDS gradually increased.

Abrupt increases in concentrations of Na+, Cl� and SO2�4 in deep

groundwater were observed around the depression cones of Profileb–b0, which indicated that overexploitation resulted in water qual-ity deterioration.

Shallow groundwater from Zone I was mainly recharged by pre-cipitation, and affected by dissolutions of halite and fluorite, pre-cipitations of calcite and dolomite, ion exchange and weakevaporation. Geochemical processes were dominated by dissolu-tions of halite and gypsum, precipitations of calcite and dolomite,evaporation, ion exchange, and sulfate reduction in weakly reduc-ing conditions of shallow groundwaters from both Zones II and III.Hydrogeochemical processes in deep groundwaters were compara-ble to those in shallow groundwater, although sulfate reductionwas stronger in deep groundwater than shallow groundwaterand evaporation was observed only in the shallow groundwater

systems. The depletion in D and 18O isotopes in deep aquiferswas related to the precipitation recharge under paleo-climate con-ditions in glacial or interglacial periods, showing that deep ground-water was mainly recharged during a past wetter climate, withvery limited renewal of groundwater. For sustainable developmentpurpose, it should be regarded as non-renewable. Any exploitationmust be highly constrained in order to make sure that the ab-stracted groundwater was recoverable.

Acknowledgements

The study has been financially supported by the National BasicResearch Program of China (the 973 program, No. 2010CB428804),the National Natural Science Foundation of China (Nos. 41172224and 41222020), the Program for New Century Excellent Talentsin University (No. NCET-07-0770), and the Chinese UniversitiesScientific Fund (Nos. 2010ZD04). Constructive comments by Editorand anonymous reviewers are gratefully acknowledged.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.jseaes.2013.03.017.

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