Hydrochemical and Isotopic Study of Groundwater in the Yinchuan Plain, China

Environ Earth Sci (2013) 69:2037–2057 DOI 10.1007/s12665-012-2040-1

ORIGINAL ARTICLE

Hydrochemical and isotopic study of groundwater in the Yinchuan plain, China

Lingfen Wang • Fusheng Hu • Lihe Yin • Li Wan • Qiusheng Yu

Received: 22 February 2012 / Accepted: 2 October 2012 / Published online: 20 October 2012 Ó Springer-Verlag Berlin Heidelberg 2012

Abstract The Yinchuan plain is located in the arid and discharge to surface water. According to the EW iso- climate zone of NW China. The western margin of the topic profile, the groundwater flow system (GFS) in the plain is the Helan mountain connecting a series of normal Yinchuan plain can be divided into local flow systems slip faults. The eastern margin of the plain connects with (LFS) and regional flow systems (RFS). Groundwater has the Yellow River and adjacents with the Ordos platform. lower TDS and higher tritium in the southern Yellow River The south of the plain is bordered by the EN fault of the alluvial plain and groundwater age ranges from 6 to Niushou mountain. The bottom of the plain is the Car- 25 years. The range of groundwater renewal rates is from boniferous, Permian, or Ordovician rocks. Based on the 11 to 15 % a-1. The depth of the water cycle is small, and analysis of groundwater hydrochemical and isotopic indi- groundwater circulates fast and has high renewal rates. cators, this study aims to identify the groundwater recharge Groundwater has higher TDS and lower tritium in the and discharge in the Yinchuan plain, China. The hydro- northern Yellow River alluvial plain. The range of chemical types of the groundwater are HCO3–SO4 in the groundwater age is from 45 to 57 years, and renewal rate is -1 west, HCO3–Cl in the middle, and Cl–SO4 in the east. The from 6 to 0.1 % a . The depth of the water cycle is larger. hydrochemical types are HCO3–SO4 in the south, HCO3– Groundwater circulates slowly and has low renewal rates. Cl and SO4–HCO3 in the middle. The hydrochemical types are complex in the north, mainly SO4–HCO3 and Cl–SO4. Keywords Hydrochemistry Isotopic Quaternary Deuterium, 18O, and tritium values of groundwater indicate Groundwater flow system that groundwater recharge sources include precipitation, bedrock fissure water, and irrigation return water. Groundwater discharges include evaporation, abstraction, Introduction

The Yinchuan plain is located in NW China. It is an L. Wang F. Hu L. Wan important industrial and agricultural base in NW China. School of Water Resources and Environment, The Yinchuan plain uses surface water from the Yellow China University of Geosciences (Beijing), Xueyuan Road 29, River for irrigation, while groundwater is the main water 100083 Beijing, China resource for industry and urban domestic usage. According L. Wang (&) to the statistics, groundwater provides up to 95 % of BGI Engineering Consultants Ltd., YangFangdian Road 15, industrial and domestic water supply. The Yinchuan plain 100038 Beijing, China is one of the driest regions in the world, and the climate is e-mail: [email protected] characterized by high temperatures and evaporation, low L. Yin rainfall, and notable drought periods (Ma et al. 2005). In Xi’an Geology Investigation Institute, Xi’an, Shanxi, China such arid and semi-arid environments, groundwater usually plays an important role for social and economic develop- Q. Yu Ningxia Institute of Geo-engineering and Reconnaissance, ment. It is suggested that a long-term, rational water usage Yinchuan, Ningxia, China guide should be set up for the Yinchuan plain as 123 2038 Environ Earth Sci (2013) 69:2037–2057 groundwater is vital for maintaining the ecosystem’s bal- ance and economic development. Groundwater acts as a receptor and information carrier in changeable ambient environments, and thus hydrochemical information can be used to characterize the behavior of groundwater systems (Han et al. 2009). There have been many studies on hydrochemical characteristics of groundwater (Fryar and Mullican 2001; Hem 1989; Garcia et al. 2001; Acheampong and Hess 1998; Sun et al. 2006; Eckardt et al. 2008; Edmunds 2009; Yin et al. 2011a). Isotopes have been widely used in the past three decades (Fritz and Fontes 1980). Isotopic techniques have proved to be an attractive tool for the identification of paleogroundwater and the origin of groundwater (Zuhair 2001; Yin et al. 2010). The ‘‘flow- systems concept’’ was first introduced by To´th (1963). Groundwater flow system (GFS) analysis has developed into a powerful tool in the field of hydrogeology. According to the hierarchy of GFS, basin scale groundwater systems can be divided into local (LFS), intermediate (IFS), and regional (RFS) flow systems (Han et al. 2009). Many researchers (Stuyfzand 1999; Winter 1999;To´th and Corbet 1986) have used the groundwater flow system theory to solving problems in hydrogeology. In order to effectively develop and manage groundwater resources, a better understanding is required of the hydrochemical and isotopic characteristics of groundwater, as well as the origin and the age (Su et al. 2009). This study examines groundwater in the Yinchuan plain and uses hydrochemistry and isotopes to study flow systems at different scales. It puts forward an integrated method for simultaneously using the isotopic and hydrochemical indicators. The specific objects of this study are to (1) identify sources of recharge; (2) identify ways of discharge; and Fig. 1 Sketch map of landscape, the Yinchuan plain (3) determine groundwater age and renewal rates using isotopes. The results of this study are helpful for aiding local meteorological date from 1959 to 2004 collected from ten governments to develop suitable water resource utilization weather stations, the mean annual temperature is 9.5 °C, strategies and policies for northwestern China. the lowest average temperature is -7.3 °C in January, and the highest average temperature is 23.5 °C in July. The annual average rainfall is 171 mm, and most rainfall con- Study area centrates in June, July, August, and September, accounting for 77 % of the annual precipitation. The maximum rainfall The Yinchuan plain is confined by the Helan mountain in is in August, and the minimum rainfall occurs in January, the west, the Niushou mountain in the south, and the Ordos February, or December. The annual potential evaporation plateau in the east. It is mainly composed of the alluvium is 1,689 mm. Most evaporation concentrates during March of the Yellow River and the pluvial deposits of the Helan to September, accounting for 81 % of the annual evapo- mountain (Fig. 1). The altitude of the Yinchuan plain ration. The annual average humidity is 55 %. According to ranges from 1,090 m to 1,400 m above sea level. In the the weight and volume method, the density of groundwater west of the Yellow River, the terrain declines from west to is approximately 1.051 g/cm3. east and from south to north. The gradient along the EW direction is large, whereas it is small along the SN direction. The Yinchuan plain can be divided into a pluvial Geology and hydrogeology plain, an alluvial flood, and an alluvial plain. The Yinchuan plain is located in an arid temperate The Yinchuan plain is mainly constituted by Quaternary zone and is of a continental climate. According to the sediments of over 1,000 m. The Center locates in Pingluo, 123 Environ Earth Sci (2013) 69:2037–2057 2039

Helan, Yinchuan, and Yongning. The deepest part is located in the west of Pingluo and Yinchun. In the Pingluo– Yinchuan area, the thickness of the Quaternary is more than 1,400 m. In the middle of Yongning and Wuzhong it becomes thinner towards the margin of the plain. Groundwater occurs in the Quaternary aquifers. The Yinchuan plain aquifer system can be divided into two types: the single unconfined aquifer, and the unconfined- confined aquifer (Fig. 2). This study focuses on the shallow unconfined groundwater (Fig. 3).

Materials and methods

Groundwater samples were collected from the shallow unconﬁned aquifer in April 2005. The following parame- ters were analyzed, including the total dissolved solid 2? 2? ? ? 2- - (TDS), pH, Ca ,Mg ,Na ,K ,SO4 , HCO3 , and Cl- (Table 1). Water samples were ﬁltered through 0.45 lm membranes on site and collected in high-density polypropylene (HDPP) bottles. Water temperature, elec- trical conductivity (EC), and pH were measured in situ using a portable instrument (HACH). The concentrations of - - 2- ? major anions (Cl ,NO3 and SO4 ) and cations (Na , K?,Ca2? and Mg2?) were measured in the laboratory

(Table 1). Sulfate (SO4) analyses of water samples were carried out using spectrophotometer, and carbonate (CO3), bicarbonate (HCO3), calcium (Ca), and magnesium (Mg) were determined by the volumetric method. Sodium (Na) and potassium (K) were determined using a ﬂame pho- tometer. The accuracy and precision of analyses were tested through running duplicate analyses on selected Fig. 2 Sketch of hydrogeology, the Yinchuan plain samples. The location of the samples was determined with

Fig. 3 Schematic diagram of the Quaternary, the Yinchuan plain

1. Clay 2. Sand 3. Gravel 4. Tertiary 5. Pre-Tertiary 6. Fault 7. Terrace

123 2040 Environ Earth Sci (2013) 69:2037–2057

Table 1 Chemical analysis of the shallow groundwater samples in the Yinchuan plain

? ? 2? 2? - 2- - Sample XY pH K Na Ca Mg Cl SO4 HCO3 TDS label (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

QPN001 635989 4318898 8.0 4.5 551.9 171.4 185.8 576.6 967.3 686.3 3,166.1 S57 621145 4313251 8.1 1.0 56.0 31.2 15.4 34.6 27.3 222.7 401.5 S60 619917 4322687 8.0 3.0 76.0 85.9 34.4 86.5 257.9 160.8 718.2 S63 645091 4312092 8.0 3.5 68.0 60.5 61.6 89.9 196.7 259.8 753.9 S69 651161 4319101 7.9 4.0 440.0 91.7 117.3 553.4 606.9 303.1 2,131.4 S9 605673 4205133 8.1 5.0 98.0 76.1 60.4 117.6 157.0 394.4 922.4 S67 636397 4321144 8.3 1.5 178.0 13.7 16.6 155.7 73.8 228.1 683.0 S72 655123 4324979 7.7 7.0 1,340.0 72.2 104.3 1,041.2 1,567.5 501.1 4,647.4 S86 632921 4261800 7.8 3.5 620.0 44.9 51.0 249.1 1,136.8 160.2 2,283.6 S68 644969 4316994 8.0 2.0 420.0 31.2 49.8 390.9 394.5 272.2 1,575.0 S70 627789 4327320 7.9 6.0 138.0 91.7 86.5 107.2 540.8 204.1 1,190.5 S79 598239 4264036 8.1 5.0 138.0 41.0 96.0 110.7 279.7 419.0 1,106.4 S66 629306 4325395 7.9 5.0 145.0 99.6 60.4 114.2 439.9 2,22.7 1,102.8 S77 656486 4331098 7.9 3.0 272.0 85.9 93.6 211.0 563.2 3,71.2 1,613.6 S76 650027 4342794 7.9 5.0 320.0 154.2 60.4 463.5 529.0 136.1 1,686.2 S85 629732 4263526 7.9 2.5 230.0 64.4 66.4 242.2 481.4 104.8 1,210.2 S65 625668 4323942 7.9 5.0 126.0 105.4 81.8 117.6 534.9 173.2 1,159.2 S73 656514 4311204 7.9 2.1 416.0 27.3 22.5 207.6 494.5 289.6 1,481.0 S8 599249 4204741 8.2 3.0 70.0 91.7 56.9 90.0 127.2 431.3 888.1 S75 640409 4335628 7.8 3.0 115.0 142.5 155.2 103.8 904.9 173.2 1,612.2 QPN005 643302 4326635 7.8 2.0 236.3 104.6 55.3 143.5 309.4 582.2 1,451.0 QPN020 635794 4269320 8.0 2.3 193.5 55.6 30.8 181.4 281.5 150.9 949.7 QPN049 635854 4296951 7.6 2.0 100.8 69.8 36.6 97.5 78.9 382.5 790.2 QPN057 608900 4306896 7.8 1.5 23.9 50.8 11.1 16.2 27.6 208.4 363.1 QPN073 619859 4256018 7.4 1.8 112.9 128.6 53.9 104.2 178.8 555.1 1,152.8 QPN079 631066 4277914 8.0 3.5 188.4 94.4 74.6 152.9 188.3 660.4 1,382.2 QPN095 618357 4291940 7.6 6.0 92.8 119.8 106.8 291.0 148.4 392.1 1,235.5 YQS007 613243 4227928 8.0 2.5 370.2 51.9 47.7 277.5 250.7 592.8 1,613.1 YQS020 589851 4197298 7.3 10.5 112.7 178.6 80.4 151.6 260.6 607.7 1,411.8 YQS027 611565 4195732 8.1 2.5 139.7 54.0 24.1 59.6 224.4 229.5 761.0 YQS038 604915 4189311 8.1 2.5 236.4 50.0 41.9 188.1 328.1 223.1 1,118.0 YQS083 609764 4234903 7.4 6.3 67.5 119.3 52.2 81.2 122.6 513.9 996.6 YQS088 616575 4244275 7.9 2.5 432.2 65.7 27.6 262.6 268.4 668.6 1,747.6 YQS089 613501 4242003 7.6 2.8 226.0 30.8 97.4 148.9 31.1 889.5 1,446.2 G6 629959 4268116 8.1 13.0 286.0 82.0 91.3 269.9 405.2 529.9 1,697.5 S18 605422 4224433 8.1 3.0 196.0 74.2 22.5 117.6 202.8 382.0 1,013.3 S43 603517 4278856 8.4 1.0 42.0 35.1 29.6 34.6 99.4 160.8 419.1 QPN002 642975 4318422 7.7 5.5 513.5 250.8 142.1 814.8 682.8 529.1 2,963.9 QPN023 643362 4296550 7.8 3.8 436.8 87.3 106.3 471.0 496.4 408.0 2,102.8 QPN046 633701 4303544 7.4 6.3 652.4 244.4 172.7 874.4 888.2 667.2 3,527.6 YQS004 617892 4229388 8.0 4.0 462.8 65.3 68.4 220.6 288.9 1,066.6 2,200.4 YQS011 606267 4211212 8.0 3.5 98.4 124.6 85.5 115.1 178.7 654.4 1,287.6 YQS016 596124 4196397 7.6 2.3 74.1 106.3 42.8 78.5 138.9 433.4 913.7 YQS041 601086 4202474 7.6 1.0 100.8 52.4 67.4 89.3 87.5 475.9 915.1 YQS048 598803 4217778 7.8 3.5 74.7 105.6 52.4 73.1 151.2 454.0 935.1 YQS084 609240 4240410 7.3 4.5 177.0 176.1 98.9 167.8 540.8 528.3 1,720.0 G11 652733 4344741 8.0 10.0 252.0 72.2 75.8 238.7 441.7 309.3 1,422.2 H18 609835 4252684 8.1 15.0 196.0 58.6 102.8 214.5 253.1 523.8 1,375.7

123 Environ Earth Sci (2013) 69:2037–2057 2041

Table 1 continued

? ? 2? 2? - 2- - Sample XY pH K Na Ca Mg Cl SO4 HCO3 TDS label (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

S10 611966 4199333 8.0 3.0 189.0 42.9 47.4 273.3 177.2 172.5 923.3 S24 588757 4236636 8.0 3.0 132.0 50.8 37.9 103.8 261.3 184.9 793.7 S29 610463 4247700 8.2 4.0 154.0 64.4 74.5 83.0 182.3 597.7 1,174.4 S33 596522 4260414 8.1 2.0 40.0 29.3 37.9 20.8 76.3 246.5 467.7 QPN010 648926 4315888 7.9 1.8 252.2 83.8 74.7 170.5 300.5 620.4 1,523.1 QPN039 616491 4284528 7.6 3.3 243.1 93.6 35.6 274.8 94.2 522.7 1,289.6 QPN053 602733 4282429 7.7 2.5 71.2 79.4 30.3 121.8 129.3 218.8 678.7 QPN078 630820 4273224 8.0 4.5 122.1 158.7 103.0 159.7 359.5 561.3 1,488.8 QPN085 625315 4288493 7.8 2.3 98.2 78.6 32.7 81.2 122.7 365.3 799.2 QPN103 619741 4243969 7.8 3.5 392.0 86.8 106.8 392.5 571.9 350.8 1,993.7 YQS002 616878 4237360 8.1 3.3 1,464.3 77.9 135.8 1,367.0 1,612.7 333.6 5,078.7 YQS023 593790 4200782 7.7 5.0 72.9 120.6 37.5 67.7 133.1 471.7 939.9 YQS050 592068 4213188 7.4 1.8 138.2 103.2 51.5 104.2 175.0 499.4 1,113.0 YQS052 589762 4206446 7.4 3.5 103.7 142.1 65.0 132.6 193.1 518.0 1,201.9 YQS053 583568 4210934 8.1 6.5 489.2 27.8 44.8 441.2 300.5 414.8 1,779.3 YQS077 595119 4238136 7.9 1.5 112.9 215.9 19.2 65.0 539.8 286.9 1,261.1 G5 627911 4258886 8.1 16.5 228.0 50.8 77.0 183.4 254.4 517.6 1,360.4 H1 623451 4248163 8.1 3.0 58.0 50.8 27.3 69.2 142.6 135.6 500.9 S17 594700 4223633 8.1 5.0 186.0 44.9 40.3 110.7 178.5 406.7 985.8 S19 614153 4221120 8.0 1.5 242.0 31.2 24.9 224.9 103.9 326.6 970.8 S21 599878 4227072 8.0 3.0 39.0 93.7 7.1 41.5 78.0 246.5 521.5 QPN003 642449 4322144 7.8 2.0 101.6 61.6 66.6 85.3 179.6 429.2 944.4 QPN029 659841 4318134 8.2 6.8 988.7 158.7 216.0 967.7 1,068.0 794.6 4,640.6 QPN032 658236 4324233 7.5 8.3 2,055.8 361.9 214.1 2,531.0 2,117.9 611.9 7,922.4 QPN051 619078 4279125 7.7 1.5 65.2 44.4 49.1 43.3 24.7 439.8 694.9 QPN058 609157 4307132 8.2 1.5 22.1 48.4 10.1 12.2 37.1 202.2 354.5 QPN066 612673 4292324 7.5 7.0 313.1 149.2 129.0 247.7 567.7 833.7 2,270.1 QPN082 626491 4284547 8.2 3.0 398.0 90.5 81.3 319.4 466.9 586.1 1,965.4 QPN107 609906 4206524 7.5 3.5 78.7 99.0 65.5 78.5 175.1 491.2 1,015.5 QPN108 579862 4239003 7.9 62.0 224.1 97.4 38.9 169.2 299.6 167.2 1,423.0 YQS021 590545 4198915 7.7 1.0 64.8 102.4 39.0 75.8 142.7 380.3 820.0 YQS063 600022 4223672 7.8 2.5 53.6 133.3 44.8 79.9 116.0 524.2 968.3 YQS092 601248 4239253 7.6 3.0 128.6 99.0 84.1 128.6 215.0 586.1 1,262.2 YQS095 602632 4253804 7.9 2.3 44.3 57.6 20.2 56.9 68.1 167.2 477.4 H10 625044 4265321 8.1 11.0 189.0 113.2 93.6 159.1 369.3 575.3 1,527.3 H14 609156 4258458 8.1 5.0 68.2 50.8 42.6 83.0 191.9 160.2 622.0 S22 607326 4231411 8.1 2.0 340.0 50.8 67.6 352.9 202.8 517.6 1,288.3 S26 609355 4252684 8.1 1.5 34.0 46.9 35.5 34.6 78.0 240.3 485.0 QPN006 649447 4333625 7.7 9.3 277.6 155.1 93.1 255.8 508.5 539.7 1,919.4 QPN009 649216 4310607 7.8 3.5 465.3 181.8 114.3 572.5 522.8 701.2 2,583.2 QPN015 637379 4308282 8.0 2.5 81.9 66.0 31.5 66.3 127.1 323.0 715.0 QPN043 632882 4314525 7.9 2.5 184.8 54.8 53.9 138.1 192.1 418.6 1,064.3 QPN061 612556 4307946 8.2 1.5 20.3 47.6 10.6 12.2 18.1 210.5 339.3 QPN080 631056 4284321 7.8 3.0 223.8 142.9 74.1 236.9 359.5 557.2 1,618.0 QPN083 603933 4281879 7.6 3.0 308.1 95.2 44.8 311.3 300.5 416.9 1,503.2 YQS014 617806 4212132 8.1 2.5 311.4 60.8 53.1 289.6 355.6 342.1 1,441.4 YQS049 594954 4213586 7.7 3.5 118.8 133.3 92.4 157.0 223.5 561.3 1,368.4 YQS056 589012 4215243 7.9 3.5 82.1 79.4 50.5 69.0 123.6 429.3 858.3

123 2042 Environ Earth Sci (2013) 69:2037–2057

Table 1 continued

? ? 2? 2? - 2- - Sample XY pH K Na Ca Mg Cl SO4 HCO3 TDS label (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

YQS058 588559 4222090 7.7 11.5 1,174.2 165.9 128.0 1,373.8 1,236.3 264.2 4,403.0 YQS081 602106 4236341 7.6 5.0 102.1 62.5 67.4 83.9 168.3 462.3 974.8 H3 624666 4318330 8.4 41.0 418.0 41.0 56.9 193.7 861.0 111.4 1,751.5 S12 592055 4216837 8.1 3.5 63.0 89.8 41.5 69.2 171.4 301.9 754.6 S2 599941 4196250 8.2 4.0 98.0 72.2 66.4 103.8 158.0 431.3 946.2 S31 582201 4252300 8.1 2.0 38.0 19.5 65.2 38.1 147.4 234.2 557.4 S47 596213 4286474 8.1 1.0 18.0 37.1 14.2 13.8 64.2 117.5 280.3 QPN018 641943 4302966 7.7 3.0 121.6 129.8 49.5 186.8 164.5 439.8 1,116.4 QPN064 608956 4299656 7.8 2.5 497.3 32.5 80.4 349.2 457.4 621.2 2,070.0 QPN074 622161 4259729 7.6 2.5 105.4 98.4 64.5 78.5 110.3 608.8 1,085.9 QPN077 626163 4278324 7.7 4.0 138.0 89.7 69.8 104.2 200.7 575.8 1,197.4 QPN104 615346 4232513 7.7 50.0 211.1 69.8 64.5 181.4 203.3 561.3 1,353.8 YQS037 607009 4182897 7.6 1.0 240.8 138.1 73.1 140.8 363.3 620.4 1,687.2 YQS059 591317 4224531 7.7 1.5 75.3 93.6 49.1 75.8 175.9 433.4 916.0 YQS090 607395 4244235 7.7 2.3 72.7 95.0 62.0 74.4 132.3 507.7 966.1 G10 650523 4333963 7.9 8.0 276.0 82.0 73.5 297.5 433.1 278.4 1,462.2 S35 618489 4253088 8.1 1.5 46.0 78.1 61.5 62.3 145.2 363.6 772.8 S42 592496 4277698 8.1 2.0 24.0 35.1 32.0 24.2 106.9 148.5 387.4 S55 647172 4298458 8.0 1.0 138.0 41.0 36.7 169.5 185.8 132.2 720.8 QPN021 638993 4276426 8.1 2.5 140.4 36.5 46.2 129.9 175.0 210.4 828.9 QPN025 648822 4302503 7.4 7.3 1,100.2 364.3 217.0 1,752.8 1,231.5 573.7 5,265.3 QPN029 659841 4318134 8.2 6.8 988.7 158.7 216.0 967.7 1,068.0 794.6 4,640.6 QPN033 654886 4320624 7.9 1.3 128.8 45.2 23.1 92.0 123.6 299.6 732.6 QPN041 633041 4307664 7.7 5.8 162.0 77.8 79.4 150.2 134.1 614.0 1,243.3 QPN060 617403 4304663 8.1 1.0 29.4 41.3 9.1 12.2 6.7 220.8 377.2 QPN076 621344 4280759 7.8 3.0 408.3 38.9 38.5 167.8 240.6 835.8 1,754.3 QPN081 634959 4285164 8.0 3.0 154.4 120.6 46.7 111.0 183.5 548.9 1,188.5 QPN093 622396 4299564 7.7 4.0 447.0 103.2 74.1 402.0 335.7 701.7 2,086.4 QPN105 616053 4224751 7.6 5.0 1,193.8 162.3 196.8 1,348.1 1,215.8 707.9 4,845.4 YQS001 625926 4248915 7.9 1.5 370.2 93.5 65.7 295.1 519.2 327.2 1,761.1 YQS013 610717 4214938 7.8 5.0 462.8 48.2 57.6 236.9 334.3 837.1 2,002.6 YQS035 610065 4187517 7.8 3.0 482.8 49.2 67.8 300.5 433.7 692.7 2,061.9 YQS043 590236 4201727 7.4 3.5 116.9 134.1 52.9 105.6 207.3 505.6 1,165.6 YQS045 596287 4207699 7.5 4.8 148.1 158.7 71.7 154.3 273.9 615.0 1,442.0 YQS075 591203 4233503 7.7 2.5 83.7 77.1 54.1 83.9 184.8 291.0 900.1 YQS087 604202 4234474 7.8 2.5 65.9 77.9 45.3 63.6 78.8 441.6 798.5 H2 635660 4328213 8.4 27.0 2,280.0 185.4 564.1 1,504.7 5,277.0 123.7 9,985.7 S13 605000 4216518 8.1 5.0 72.0 117.1 55.7 79.6 158.0 486.8 992.2 S14 607003 4214691 8.1 4.0 92.0 80.0 103.1 121.1 240.8 482.1 1,139.9 S40 613962 4261341 8.2 33.0 129.0 103.5 90.1 121.1 203.6 677.8 1,370.0 S49 627150 4290757 8.0 2.0 174.0 46.9 59.3 110.7 317.6 296.9 1,022.8 QPN016 644043 4304980 7.9 3.5 97.3 106.1 44.5 111.0 105.8 475.9 966.8 QPN055 602912 4299520 7.7 1.8 63.1 87.3 18.8 65.0 131.2 255.9 666.1 QPN056 605311 4303338 7.6 2.0 53.0 109.5 18.8 58.2 136.9 282.7 736.9 QPN057 608900 4306896 7.8 1.5 23.9 50.8 11.1 16.2 27.6 208.4 363.1 YQS076 594086 4235216 8.1 3.0 150.6 60.1 40.4 132.6 264.6 224.9 890.8 YQS086 614113 4252332 7.7 3.0 132.8 112.8 77.8 117.8 213.0 641.8 1,321.4 H19 599401 4240753 8.2 9.5 388.0 48.8 86.3 297.6 319.8 690.1 1,853.8

123 Environ Earth Sci (2013) 69:2037–2057 2043

Table 1 continued

? ? 2? 2? - 2- - Sample XY pH K Na Ca Mg Cl SO4 HCO3 TDS label (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

S27 587619 4248616 8.1 4.0 114.0 54.7 66.4 96.9 268.8 283.5 906.5 S45 632613 4278610 7.8 8.0 540.0 160.1 154.1 806.0 707.8 402.1 2,794.5 S54 639124 4302053 8.1 1.5 94.0 29.3 23.7 62.3 104.2 216.5 543.7 S61 624680 4319281 8.1 2.0 72.0 37.1 13.0 48.4 59.0 204.1 444.2 S62 645961 4306973 8.0 4.0 256.0 91.7 86.5 283.6 390.8 402.1 1,526.5 S78 583798 4219232 7.8 5.0 432.0 23.4 111.4 342.5 779.7 172.5 1,890.0 QPN030 650522 4338022 8.3 9.5 144.4 57.1 63.5 166.2 169.3 359.1 1,028.4 QPN054 601058 4293001 7.4 2.5 141.0 135.7 30.8 123.2 271.0 379.7 1,138.6 YQS015 617155 4213129 7.7 3.5 193.3 120.2 101.7 227.4 280.9 658.7 1,613.2 YQS030 607942 4204381 8.1 3.5 250.2 84.1 62.1 121.8 252.0 654.4 1,196.7 H16 622582 4258207 8.1 13.0 142.0 56.6 100.5 159.2 271.7 443.7 1,639.2 H17 620061 4252811 8.4 10.0 290.4 52.7 105.2 283.7 329.6 554.6 2,062.3 H8 614204 4283515 8.0 18.0 402.0 27.3 138.7 304.4 610.5 544.4 789.0 S34 611571 4255528 7.8 2.0 158.0 44.9 29.6 173.0 145.1 220.4 1,898.7 QPN011 649494 4310612 7.8 3.5 308.6 127.6 84.1 270.7 389.4 692.7 1,467.9 QPN013 641341 4310929 8.0 2.8 153.0 144.7 76.9 134.0 335.2 599.2 822.2 QPN024 646958 4295283 8.4 2.3 160.4 33.3 28.4 115.1 106.5 308.1 1,425.5 QPN065 611720 4296430 7.5 4.0 247.6 91.3 51.0 189.5 244.4 588.2 1,434.3 YQS029 601081 4205860 7.5 3.0 120.3 121.4 55.3 97.5 205.4 505.7 1,130.9 YQS054 584628 4206393 7.7 2.0 268.7 112.7 109.2 227.4 407.0 650.1 1,834.6 YQS058 588559 4222090 7.6 2.5 75.3 92.9 65.4 78.5 143.6 528.3 1,005.8 YQS085 611261 4244715 7.5 2.3 61.9 143.7 49.7 101.5 117.7 491.2 1,023.2 H13 598404 4263514 8.4 5.0 134.0 33.2 56.7 152.2 214.4 197.2 821.2 H4 607928 4299411 8.4 4.0 164.0 42.9 48.6 138.4 222.7 259.8 904.4 S1 615211 4192268 18.3 2.0 206.0 17.6 23.7 114.2 148.2 320.4 848.2 S11 582720 4215683 8.0 3.0 192.0 46.9 59.3 124.6 358.7 289.6 1,093.1 S50 636378 4291135 7.9 5.0 320.0 138.6 96.0 345.9 602.3 383.5 1,908.5 QPN017 647058 4307690 7.8 3.3 123.8 118.7 52.6 119.1 154.7 560.9 1,156.7 QPN042 630825 4313058 11.0 9,237.5 575.4 1,058.5 11,978.3 7,180.0 452.6 30,515.6 QPN052 598467 4276080 7.8 4.0 117.7 55.6 36.6 104.2 163.6 301.3 815.5 QPN062 612635 4307858 7.8 2.0 153.0 55.6 36.6 215.2 116.0 245.6 842.7 QPN069 620156 4267682 7.4 3.0 87.3 94.4 91.9 89.3 161.7 590.2 1,135.2 QPN071 632723 4264116 7.6 3.0 136.0 106.3 41.9 166.5 87.5 499.4 1,060.9 QPN089 628207 4296890 8.1 3.8 118.8 88.1 64.5 124.5 185.4 437.5 1,038.2 QPN091 629932 4304092 7.6 40.0 543.1 69.8 25.0 369.5 341.8 282.7 2,094.0 QPN106 618780 4206670 8.3 1.0 91.9 25.2 16.2 66.3 75.9 158.9 485.2 YQS022 596893 4199472 7.5 2.0 105.2 130.2 83.7 105.6 186.4 605.5 1,269.4 YQS036 612762 4185078 8.1 1.5 108.9 84.1 107.8 102.9 237.8 539.7 1,217.9 YQS079 598186 4232416 8.1 3.8 97.9 87.7 67.9 92.0 162.4 515.9 1,046.7 G4 625033 4254692 8.1 13.0 216.0 62.5 73.5 193.8 269.6 456.0 1,301.3 S16 584051 4223183 7.8 3.0 392.0 80.0 67.6 380.6 631.9 160.2 1,733.9 S37 595146 4261926 8.1 2.0 38.0 39.0 36.7 20.8 68.4 271.1 491.1 S48 610798 4290823 8.1 1.0 48.0 31.2 11.9 34.6 49.1 154.7 344.6 QPN007 647903 4341648 7.7 6.5 349.7 293.0 108.0 670.0 675.7 318.7 2,527.9 QPN031 656030 4334986 7.4 8.8 2,055.8 373.8 273.3 2,070.8 2,594.3 964.6 8,363.9 QPN038 614155 4282951 7.9 3.3 675.0 66.7 89.5 706.5 646.7 333.6 2,540.1 QPN045 636613 4312423 8.4 4.3 441.0 62.7 69.8 251.8 316.7 728.8 1,946.9 QPN048 637319 4299708 2.5 149.9 80.2 57.7 101.5 97.0 628.9 1,143.8

123 2044 Environ Earth Sci (2013) 69:2037–2057

Table 1 continued

? ? 2? 2? - 2- - Sample XY pH K Na Ca Mg Cl SO4 HCO3 TDS label (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

QPN068 620857 4269769 7.7 1.5 72.6 90.5 20.7 55.5 141.7 321.9 721.9 QPN072 627510 4258235 7.8 3.3 534.2 92.9 77.5 475.1 333.8 842.0 2,380.4 QPN094 624143 4295071 7.5 5.0 237.1 111.1 73.1 169.2 350.9 575.8 1,541.7 QPN102 629628 4252017 8.4 1.5 527.7 90.9 94.5 462.9 810.2 260.0 2,300.6 YQS008 616071 4224697 8.7 7.0 350.3 34.1 28.3 249.0 309.4 299.6 1,327.1 YQS032 618216 4191137 8.3 2.0 201.7 43.7 40.4 232.8 183.5 170.0 911.1 YQS040 604602 4193408 7.5 3.5 120.5 58.7 71.2 85.3 117.9 533.3 1,010.0 YQS078 598709 4235060 7.6 4.5 283.6 64.9 141.7 208.4 356.0 908.0 1,986.0 YQS091 611261 4244715 7.4 10.5 177.0 69.0 111.2 169.2 2.0 982.3 1,538.8 H12 604082 4270127 7.8 13.0 620.0 72.2 126.5 477.5 1,040.5 345.1 2,707.0 H22 582577 4210438 8.0 5.0 620.0 66.4 99.5 477.5 656.2 653.2 2,595.4 H6 625597 4293208 8.1 18.0 400.0 68.3 133.9 335.5 584.5 624.8 2,175.0 S200 623029 4324895 7.9 5.0 150.0 156.2 72.3 124.5 669.4 167.0 1,362.1 QPN004 637313 4326484 7.7 13.5 475.9 155.1 139.4 457.5 718.3 743.7 2,727.6 QPN012 644796 4313657 7.7 4.3 201.1 142.4 70.6 170.5 336.1 611.9 1,560.1 QPN026 650041 4303748 7.8 7.8 1,326.3 393.6 307.0 1,881.3 1,895.3 531.2 6,367.5 QPN034 655659 4316996 7.5 5.8 771.8 307.9 167.0 1,455.0 660.9 484.4 3,880.7 QPN084 621512 4287446 7.6 3.5 499.9 117.5 153.5 514.3 564.9 813.1 2,684.1 QPN086 622501 4291015 7.8 1.3 60.9 80.2 33.2 63.6 114.1 324.0 690.4 QPN090 628055 4301485 7.9 2.3 72.3 66.7 26.0 74.4 91.3 282.7 631.4 YQS060 589562 4226915 7.9 2.8 104.2 84.9 33.7 129.9 208.3 243.5 824.5 YQS096 606876 4255911 7.4 5.5 101.9 109.6 65.9 86.6 144.0 606.7 1,151.5 YQS097 602943 4257241 7.7 3.8 98.2 43.8 96.5 67.7 111.9 619.1 1,062.2 G16 607439 4231122 8.0 6.0 211.0 70.3 60.3 193.8 293.6 363.6 1,224.1 G2 601708 4218105 8.1 5.0 105.0 78.1 68.7 90.0 217.9 1,005.2 H7 624831 4287547 8.3 9.0 209.0 29.3 77.0 176.4 321.5 315.5 1,149.2 S23 611716 4224121 8.1 3.0 180.0 70.3 54.5 280.3 101.4 348.1 1,065.9 S44 619879 4280863 8.0 3.0 121.0 113.2 85.3 124.5 392.4 377.4 1,234.5 S52 616251 4299211 8.1 1.0 46.0 29.3 15.4 20.8 57.9 185.6 366.0 QPN027 654360 4306718 7.7 3.3 537.2 63.5 61.6 373.6 466.9 662.9 2,233.3 QPN070 627091 4265390 7.5 2.5 105.4 81.7 43.8 102.9 93.2 454.0 904.6 YQS012 611933 4210973 7.7 4.0 73.9 96.4 52.2 74.4 90.7 539.7 946.1 YQS019 592031 4196630 7.5 1.0 131.8 128.6 77.9 162.4 264.4 512.1 1,294.6 YQS024 602198 4199204 7.6 5.5 155.7 127.0 54.4 170.5 157.9 560.9 1,248.1 YQS042 586863 4199766 7.4 4.5 158.2 128.6 78.4 150.2 290.1 524.2 1,378.0 YQS046 601545 4210742 7.6 5.0 162.3 211.1 69.8 207.1 391.8 584.0 1,650.3 YQS061 595634 4230068 7.3 2.5 88.6 142.9 52.0 125.9 191.2 497.4 1,122.1 YQS094 600394 4248337 0.0 2.3 75.0 51.9 38.9 83.9 151.7 194.0 647.5 G7 630906 4273497 8.0 41.0 480.0 89.8 104.3 425.5 679.0 494.9 2,330.6 G8 633650 4289940 8.3 9.5 312.0 66.4 94.8 290.6 487.0 371.2 1,669.1 G9 654134 4331716 8.3 9.0 392.0 78.1 96.0 394.3 592.5 315.5 1,900.4 H15 616252 4258344 8.2 24.0 396.0 72.2 69.7 380.6 214.7 714.8 1,884.1 S15 616850 4203248 8.1 2.0 86.0 27.3 26.1 90.0 112.2 141.7 505.4 S20 592131 4231150 8.1 2.0 32.0 29.3 35.6 27.7 86.6 178.7 406.8 S25 607788 4238161 8.1 3.5 74.0 93.7 46.2 79.6 81.1 468.3 861.6 S4 586783 4202212 8.1 3.5 64.0 87.8 60.4 65.7 227.5 326.6 848.4 S41 622620 4263398 8.2 3.0 80.0 82.0 49.8 55.4 128.2 456.0 869.1 S46 588691 4290736 8.0 1.0 14.0 44.9 16.6 20.8 82.8 111.4 307.4

123 Environ Earth Sci (2013) 69:2037–2057 2045

Table 1 continued

? ? 2? 2? - 2- - Sample XY pH K Na Ca Mg Cl SO4 HCO3 TDS label (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

QPN028 654903 4310006 7.7 2.8 321.9 115.1 90.9 289.6 473.6 541.8 1,894.4 QPN050 633335 4290123 7.5 3.0 245.3 127.8 63.5 163.8 276.7 733.0 1,638.2 QPN059 624171 4311018 8.1 0.8 61.9 23.8 8.2 20.3 7.6 245.6 386.0 QPN063 612683 4303861 8.0 0.8 28.5 42.1 9.6 13.5 15.2 200.2 333.7 QPN067 616599 4267541 7.4 4.3 151.9 100.8 84.7 117.8 153.1 755.3 1,382.7 QPN092 624679 4306828 8.0 0.8 745.5 54.8 14.0 192.2 262.5 487.0 1,376.5 YQS025 607402 4199520 7.6 7.0 291.1 69.8 86.6 173.3 310.0 658.7 1,644.8 YQS039 605810 4191229 7.9 13.8 1,711.2 286.5 309.9 1,326.4 2,957.6 881.8 7,506.1 YQS062 601806 4230303 7.9 2.5 71.8 104.0 28.9 39.3 106.5 423.1 792.2 YQS074 586910 4253232 8.0 3.5 139.5 43.8 35.4 70.4 211.1 286.9 853.7 YQS082 604202 4234474 7.8 2.0 82.5 138.8 45.8 97.5 163.4 518.0 1,068.9 S3 600871 4191382 7.9 5.5 484.0 95.7 101.9 484.4 736.6 308.1 2,235.0 S32 592585 4259576 8.1 4.0 48.0 80.0 40.3 58.8 143.6 283.5 673.6 S56 607302 4307789 8.0 2.0 42.0 93.7 21.3 69.2 184.3 148.5 576.7 QPN008 655227 4350643 7.7 12.3 382.5 116.5 72.9 315.4 531.6 467.4 19,400.0 QPN022 640867 4287221 7.7 9.0 237.9 121.4 65.4 246.3 364.2 463.2 1,529.7 QPN037 614165 4280464 7.5 1.5 151.9 78.6 73.6 94.7 117.9 650.2 1,193.9 QPN047 636483 4301326 8.0 7.5 720.7 261.1 160.7 1,074.7 833.1 614.0 3,694.4 YQS006 613143 4216685 7.5 3.8 151.8 135.0 110.2 162.4 194.7 892.4 1,677.1 YQS018 597873 4194642 7.4 12.0 168.0 167.5 99.1 213.9 355.7 597.0 1,671.5 YQS044 593637 4205141 7.7 4.0 100.1 115.9 45.2 93.4 190.2 445.8 1,009.5 YQS047 602942 4213968 7.7 4.5 122.6 141.3 66.4 115.1 253.9 584.0 1,306.1 YQS093 618966 4249303 7.9 2.0 64.8 44.6 48.7 79.9 136.2 218.8 642.6 H5 616251 4299211 8.3 16.5 548.0 31.2 119.7 470.4 755.8 377.4 2,333.0 S36 626555 4254492 8.1 3.0 92.0 97.6 64.0 83.0 224.2 431.3 1,011.0 S51 602400 4301472 8.0 3.0 36.0 42.9 16.6 27.7 71.9 160.8 371.8 S58 627186 4314922 8.1 1.0 89.0 15.6 10.7 55.3 30.6 198.0 412.8 S59 635534 4310353 8.1 1.0 198.0 39.0 37.9 159.1 230.0 259.8 938.1 S71 648194 4333460 7.7 8.5 1,360.0 288.9 218.0 1,670.7 1,801.0 383.5 5,748.2

a global positioning system (GPS) (Kansas, USA). The tritium were electrolytically enriched and were analyzed location and results of water samples are shown in Fig. 4 using a Quantulus-1220 Liquid Scintillation Beta Spec- and Table 1. trometer. The results were reported as tritium units with a Samples were taken for isotopic analysis during October typical error of ±0.1–0.2 TU (Eichinger 1980). The results and November 2004. 102 samples for 18O, deuterium are shown in Table 2. (D) and tritium (T) measurements were collected in glass In the paper, all contours maps were drawn in Arcgis 9.3 bottles with gas-tight caps. The 18O, deuterium, and tritium with the inverse distance weighting method, and were analyses were performed in the State Key Laboratory of modiﬁed manually later. Geological Processes and Mineral Resources, China University of Geosciences. Samples for stable isotope analysis (18O, and deuterium) were measured by an isotope Results and discussion ratio mass spectrometry (VG Micromass 602C). The 18O and deuterium values were measured relative to interna- Hydrochemical characteristics tional standards that were calibrated using V-SMOW (Vienna Standard Mean Ocean Water) and reported in The results of groundwater chemical analysis are shown in conventional d (%) notation. The analytical precision is Table 1. pH varies from 7.3 to 8.7, indicating an alkaline ±0.1 % for 18O and ±1 % for deuterium. Samples for nature. TDS ranges from 280.30 to 1,9400.02 mg/l with a

123 2046 Environ Earth Sci (2013) 69:2037–2057

Ca–Na–HCO3) occupy over 19 % of the area. Nearly 60 % of the area is covered by the Na? dominated groundwater

types, such as Na–Mg–SO4–Cl, Na–HCO3, Na–Cl, and Na–SO4. Ca–SO4 and Mg–SO4 only cover about 4 %. Finally, the groundwater hydrochemical types in the study area are identiﬁed spatially and indicate an obvious zonation as shown in Fig. 5: In the west of the Yellow River, TDS of groundwater changes from low to high along the direction of the groundwater ﬂow from SW to NE.

The Groundwater hydrochemical type is mainly HCO3– SO4–Mg–Na in the south. In the middle (Yinchuan city), the hydrochemical type is of multivariate distribution, such

as HCO3–SO4–Ca–Mg, SO4–HCO3–Ca–Na, and HCO3– Cl–Mg–Na. In the north, the hydrochemical type is mainly

Cl–SO4–Na–Ca with increasing TDS. In the east of the Yellow River, the range of the TDS is 1–3 g/l in the

south. The hydrochemical type is SO4–Cl–Na–Mg or Cl–SO4–Na–Ca. In the middle and north, the TDS is higher than 3 g/l. The hydrochemical type changes from HCO3– SO4–Ca–Mg to SO4–Cl–Na–Mg or Cl–SO4–Na–Ca.

Groundwater age dating

Tritium, with its half-life of 12.32 years (Lucas and Unterweger 2000) has been widely used for the estimation of recent groundwater age and renewal rates. In some cases, investigators calculated groundwater age from tri- Fig. 4 Site map of the Yinchuan plain showing the sampling locations tium concentrations (Weissmann et al. 2002; Craig and Johnson 2008; LaBolle et al. 2006; Cook and Herczeg 1998). Several models have been developed to esti- mean of 1,683 mg/l. According to the TDS classiﬁcation, mate groundwater age and renewal rates using tritium 64.68 % of groundwater belongs to the brackish type (Maloszewski and Zuber 1996). In this study, the expo- (TDS [ 1,000 mg/l), and the remaining are fresh water nential distribution function (Fontes 1983; Yurtsever 1983) (TDS \ 1,000 mg/l). The concentrations of Ca, Mg, Na, was applied. The required tritium input function for this and K range from 13.6 to 575.35, 7.11 to 1058.51, 14 to simulation was taken from the available tritium records of 9237.51, and 0.75 to 62.00 mg/l with a mean of 95.01, the Yinchuan station, the closest IAEA network station to 75.37, 297.60, and 5.28 mg/l, respectively. Their ionic the study area. The IAEA’s network in Yinchuan can pro- concentrations in mmol/l are 12, 16.3, 71, and 0.7 %. The vide the monthly tritium concentration of precipitation from order of the abundance is Na [ Mg [ Ca [ K. The dis- 1986. The values of tritium during the period of 1960–1986 solved anions, Cl, SO4, and HCO3, vary between 12.18 to were estimated from the Doney model (Doney et al. 1992). 11978.31, 1.95 to 7180.00, and 104.75 to 1066.61 mg/l, The tritium values in precipitation during 1953–1959 were with a mean of 295.81, 386.15, and 433.34 mg/l, respec- approximated from the correction with the data of Ottawa, tively. Their ionic concentrations are 45.5, 20.4, and Canada that has the longest tritium records globally. 34.1 %, respectively. The order of the abundance is The tritium input function of the Yinchuan station is shown

Cl [ HCO3 [ SO4. Ten hydrochemical types have been in Fig. 6. identified (Table 3). Hydrochemical types are useful Groundwater in the Yinchuan plain receives recharge information in comparing their distribution (Uphori and from lateral flow and vertical infiltration (Yu 2005), so the Toth 1989; Saha et al. 2010). The most frequently observed exponential-piston model (EMP) was chosen to identify type is Na–HCO3 followed by Na–Cl (Table 3). Spatially, groundwater age. The isotopic model FLOWPC3.1 was 2? - Mg and HCO3 are the dominated types, e.g. Mg–Na– applied to calculate groundwater age (Maloszewski and HCO3 and Mg–Ca–HCO3, cover about 17 % of the area. Zuber 1996). The age distribution function is expressed as 2? - Ca and HCO3 dominated types (Ca–Mg–HCO3 and follows:

123 Environ Earth Sci (2013) 69:2037–2057 2047

Table 2 Results of the isotopic analysis for surface and groundwater Table 2 continued samples from the Yinchuan plain Label XY Depth dD(%) d18O(%) T (TU) Label XY Depth dD(%) d18O(%) T (TU) DTS54 639124 4302053 113 -80.58 -11.35 6.11 Surface water samples DTS50 636378 4291135 20 -76.67 -9.07 16.08 DTG11 652733 4344741 0 -71.43 -8.33 6.52 DTS48 610798 4290823 150 -83.69 -11.46 DTG9 654134 4331716 0 -67.18 -8.62 9.81 DTS49 627150 4290757 -81.26 -10.32 DTG10 650523 4333963 0 -66.01 -8.92 8.62 DTS44 619879 4280863 30 -79.21 -10.31 23.05 DTH3 624666 4318330 0 -40.86 -4.11 15.66 DTS45 632613 4278610 20 -61.61 -8.29 0.72 DTH4 607928 4299411 0 -59.85 -7.48 22.75 DTS46 588591 4290736 -74.76 -10.05 10.64 DTH2 635660 4328213 0 -22.83 -0.75 21.31 DTS42 592496 4277698 -74.83 -10.67 DTH5 616251 4299211 0 -17.51 -1.53 16.94 DTS47 596213 4286474 -72.83 -10.56 DTG8 634650 4289940 0 -53.24 -7.77 15.25 DTS43 603517 4278856 -80.1 -11.26 DTH6 625597 4293208 0 -54.23 -6.44 21.48 DTS74 642474 4287736 110 -62.73 -8.27 DTH7 624831 4287547 0 -40.24 -4.42 16.74 DTS55 647172 4298458 120 -77.45 -9.28 DTH8 614204 4283515 0 -44.09 -1.93 17.59 DTS73 656514 4311204 -75.01 -9.16 22.89 DTG7 630906 4273497 0 -74.31 -9.78 DTS24 588757 4236636 100 -77.21 -9.29 1.97 DTH10 625044 4265321 0 -59.92 -7.89 14.13 DTS16 584051 4223183 30 -78.69 -10.72 0.09 DTH1 623451 4248163 0 -72.69 -8.97 23.39 DTS78 583798 4219232 85 -76.17 -9.79 16.25 DTH22 582577 4210438 0 -60.14 -8.07 7.08 DTS6 556972 4211107 70 -75.63 -9.32 36.05 DTG2 601708 4218105 0 -63.05 -8.82 16.86 DTS11 582720 4215683 -78.51 -9.43 26.31 DTG6 629959 4268116 0 -82.12 -8.95 6.34 DTS4 586783 4202212 64 -69.5 -9.48 7.42 DTG5 627911 4258886 0 -53.92 -4.65 15.32 DTS12 592055 4216837 -73.37 -10.17 17.95 DTG4 625033 4254692 0 -58.71 -7.3 0.2 DTS17 594700 4223633 220 -76.48 -10.66 DTH15 616232 4258344 0 -63.5 -6.27 DTS13 605000 4216518 -70.99 -9.12 10.17 DTH14 609156 4258458 0 -70.11 -7.47 7.33 DTS18 605422 4224433 -75.84 -9.98 16.46 DTH18 609835 4252684 0 -39.59 -2.48 5.81 DTS21 599878 4227072 -79.83 -10.46 1.23 DTH17 620061 4252811 0 -28.13 -2.07 7.81 DTS20 592131 4231150 20 -88.6 -11.43 5.76 DTH16 622582 4258207 0 -53.32 -3.54 12.45 DTS27 587619 4248626 22 -79.66 -10.1 11.9 DTH19 599401 4240753 0 -30.08 -3.07 1.16 DTS31 582201 4252300 230 -76.76 -10.44 DTG16 607439 4231122 0 -82.96 -9.89 DTS37 595146 4261926 160 -73.38 -10.85 DTH12 604082 4270127 0 -32.79 -4.28 9.59 DTS33 596522 4260414 70 -83.78 -11.13 3.29 DTH13 598404 4263514 0 -40.63 -6.69 5.3 DTS32 592585 4259576 -82.79 -10.33 45.49 Groundwater samples DTS79 598239 4264036 40 -73.94 -8.92 20.07 DTS70 627789 4327320 80 -76.47 -9.72 3.85 DTS40 613962 4261341 18 -78.46 -9 18.67 DTS75 640409 4335628 150 -75.58 -9.23 DTS41 622620 4263398 90 -84.92 -10.29 13.14 DTS76 650027 4342794 80 -73.11 -8.98 DTS85 629732 4263526 200 -90.91 -9.38 4.96 DTS68 644969 4316994 58 -78.94 -10.31 DTS86 632921 4261800 350 -91.29 -9.64 DTS69 651161 4319101 60 -75.4 -10.24 15.26 DTS36 626555 4254429 12 -67.26 -8.19 11.34 DTS72 655123 4324979 40 -68.56 -8.89 17.99 DTS3 600871 4191382 100 -83.04 -9.67 19.81 DTS77 656486 4331098 12 -68.69 -9.51 39.82 DTS2 599941 4196250 92 -84.61 -10.23 7.38 DTS71 648194 4333460 30 -78.26 -10.59 DTS8 599249 4204741 40 -79.28 -8.96 13.7 DTS67 636397 4321144 40 -79.3 -10.47 DTS10 611966 4199333 100 -75.61 -8.22 DTS61 624680 4319281 40 -75.5 -10.6 DTS1 615211 4192268 80 -88.22 -9.24 DTS63 645091 4312092 80 -77.4 -11.73 14.66 DTS15 616850 4203248 300 -81.2 -8.55 0.49 DTS62 645961 4306973 50 -76.61 -10.47 10.28 DTS19 614153 4221120 -80.63 -9.43 3.23 DTS51 602400 4301472 100 -74.34 10.24 DTS23 611716 4224121 12 -88.89 -10.44 10.43 DTS56 607302 4307789 70 -76.05 -9.76 32.74 DTS35 618489 4253088 120 -94.64 -10.6 DTS57 621145 4313251 -88.8 -11.72 DTS29 610463 4247700 15 -78.65 -8.66 6.82 DTS200 623029 4324895 200 -68.73 -8.6 14.85 DTS34 611571 4255528 120 -107.69 -11.58 DTS65 625668 4323942 100 -75.94 -9.1 8.98 DTS14 607003 4214691 15 -75.83 -8.94 4.12 DTS66 629306 4325395 80 -72.71 -9.08 10.31 DTS9 605673 4205133 120 -82.49 -9.4 5.87 DTS60 619917 4322687 -76.24 -9.12 0.55 DTS22 607326 4231411 -83.82 -9.48 24.2 DTS52 616251 4299211 -80.56 -11.56 DTS25 607788 4238161 17 -61.5 -8.76 17.41 DTS58 627186 4314922 120 -82.66 -11.71 2.54 DTS26 609355 4239637 140 -89.12 -10.72 DTS59 635534 4310353 150 -83.73 -11.21

123 2048 Environ Earth Sci (2013) 69:2037–2057

Table 3 Chemical compositions of different hydrochemical facies (mg/l) Min Max Average St.Dev. Dev. Coeff Var % Sample No

Ca–Mg-HCO3 K 1 12 3.604 2.788 77.347 92 24 Na 14 167.95 78.065 33.651 43.107 92 24 Ca 37.09 178.56 111.268 34.655 31.146 79 24 Mg 14.22 99.11 51.145 18.629 36.425 86 24 Cl 13.84 213.85 90.611 43.316 47.804 94 24

SO4 64.17 355.67 157.315 69.709 44.312 82 24

HCO3 111.35 607.67 447.746 135.371 30.234 82 24 pH 7.3 8.14 7.638 7.872 103.066 10 24 TDS 280.3 1,671.5 962.742 311.147 32.319 83 24

Ca–Na–HCO3 K 0.75 5 2.611 1.159 44.382 85 27 Na 20.34 162.29 79.308 45.36 57.195 87 27 Ca 41.27 211.09 97.698 42.675 43.68 80 27 Mg 7.11 76.91 32.946 21.405 64.971 91 27 Cl 12.18 207.08 78.758 54.779 69.553 94 27

SO4 6.66 391.81 136.994 98.579 71.959 98 27

HCO3 160.84 614.98 361.061 153.08 42.397 74 27 pH 7.35 8.18 7.725 7.988 103.415 10 27 TDS 333.73 1,650.31 793.346 370.044 46.643 80 27

Ca–SO4 K 1.5 5 3.167 1.366 43.145 70 6 Na 42 176.95 102.633 53.383 52.013 76 6 Ca 50.75 215.89 129.752 62.82 48.416 76 6 Mg 19.19 98.91 45.558 32.568 71.486 81 6 Cl 64.97 167.83 97.03 41.128 42.387 61 6

SO4 142.6 669.36 389.11 221 56.796 79 6

HCO3 135.56 528.31 237.84 152.427 64.088 74 6 pH 7.34 8.09 7.784 7.839 100.7 9 6 TDS 500.92 1,720 1,023.148 494.408 48.322 71 6

Mg–Ca–HCO3 K 1.5 6 2.99 1.015 33.944 75 24 Na 24 151.83 80.008 30.79 38.483 84 24 Ca 29.28 158.72 90.563 33.039 36.482 82 24 Mg 31.99 110.2 66.552 22.587 33.939 71 24 Cl 20.76 291 91.19 57.344 62.884 93 24

SO4 68.35 359.48 161.404 61.683 38.217 81 24

HCO3 148.46 892.38 447.36 171.418 38.318 83 24 pH 7.4 8.15 7.773 7.96 102.405 9 24 TDS 387.36 1,677.14 968.912 329.451 34.002 77 24

Mg–Na–HCO3 K 1 33 5.163 6.695 129.67 97 23 Na 38 177.01 104.056 35.932 34.532 79 23 Ca 19.52 112.82 65.799 25.281 38.422 83 23 Mg 29.63 111.21 74.553 22.015 29.529 73 23 Cl 20.76 169.19 96.182 37.722 39.22 88 23

SO4 1.95 279.68 157.546 73.077 46.385 99 22

HCO3 160.84 982.32 470.817 191.094 40.588 84 23 pH 7.38 8.36 7.807 7.964 102.016 12 23 TDS 419.08 1,639.21 1,025.153 321.99 31.409 74 23

123 Environ Earth Sci (2013) 69:2037–2057 2049

Table 3 continued

Min Max Average St.Dev. Dev. Coeff Var % Sample No

Mg–SO4 K 3 6 4.333 1.211 27.948 50 6 Na 68.2 138 113.7 23.946 21.061 51 6 Ca 50.75 142.5 93.047 35.411 38.057 64 6 Mg 42.55 155.24 86.292 37.645 43.626 73 6 Cl 83.04 124.52 105.508 14.786 14.014 33 6

SO4 191.93 904.85 472.262 253.82 53.746 79 6

HCO3 160.21 377.35 228.595 85.495 37.4 58 6 pH 7.76 8.13 7.952 8.435 106.08 5 6 TDS 621.99 1,612.2 1,120.798 333.308 29.738 61 6 Na–Cl K 1 40 5.769 6.188 107.274 98 40 Na 86 9,237.51 843.964 1,450.701 171.891 99 40 Ca 13.66 575.35 151.863 133.072 87.627 98 40 Mg 16.59 1,058.51 134.966 168.704 124.997 98 40 Cl 89.96 11,978.31 1,030.86 1,877.077 182.088 99 40

SO4 73.78 7,180 860.372 1,193.661 138.738 99 40

HCO3 132.24 964.62 421.61 211.683 50.208 86 40 pH 7.37 8.7 7.79 7.996 102.645 15 39 TDS 505.38 3,0515.6 3,531.667 4,809.501 136.182 98 40

Na–HCO3 K 0.75 50 5.038 6.752 134.016 98 72 Na 46 745.46 234.611 139.715 59.552 94 72 Ca 15.62 149.19 73.939 34.266 46.344 90 72 Mg 8.18 141.72 58.675 29.154 49.688 94 72 Cl 20.3 475.07 172.176 94.985 55.167 96 72

SO4 7.61 567.74 229.126 122.792 53.591 99 72

HCO3 154.65 1,066.61 533.727 198.996 37.284 86 72 pH 0 18.33 1.851 0.926 50 100 71 TDS 344.6 2,380.37 1,332.677 519.168 38.957 86 72

Na–Mg–SO4–Cl K 1 41 8.692 8.85 101.817 98 26 Na 134 2,280 500.937 467.766 93.378 94 26 Ca 23.42 286.48 93.093 56.694 60.9 92 26 Mg 37.92 564.06 116.753 105.946 90.743 93 26 Cl 132.64 1,504.67 427.47 314.305 73.527 91 26

SO4 214.36 5,277.04 849.945 1,037.093 122.019 96 26

HCO3 104.75 881.76 362.383 193.806 53.481 88 26 pH 7.66 8.4 7.968 8.318 104.393 9 26 TDS 821.15 19,400.02 3,058.962 3,883.645 126.96 96 26

Na–SO4 K 2 62 9.957 14.944 150.086 97 21 Na 104.21 1,340 321.617 267.299 83.111 92 21 Ca 27.33 155.05 66.946 32.409 48.41 82 21 Mg 22.52 138.65 66.492 33.205 49.938 84 21 Cl 59.55 1,041.16 233.768 200.191 85.637 94 21

SO4 208.27 1,567.53 499.81 332.779 66.581 87 21

HCO3 111.35 624.79 333.052 160.321 48.137 82 21 pH 7.68 8.37 7.961 8.342 104.792 8 21 TDS 761.01 4,647.43 1,512.793 866.536 57.281 84 21

123 2050 Environ Earth Sci (2013) 69:2037–2057

Fig. 5 Distribution of TDS (g/l) and hydrochemical types

0 0 1 Groundwater age is showed in Fig. 7. In the Helan 0 ðÞg=tt expðÞgt =tt þ g 1 ; t ðÞ1 g tt gtðÞ¼ 0 1 0; t \ðÞ1 g tt mountain pluvial plain, the range of groundwater tritium age is from 15 to 50 years. The age is older in the middle, ð1Þ about 45–50 years. The age in the south and north is where g is the ratio of total volume of ﬂowing water and younger than in the middle, indicating an abundance the volume of exponential water of the system, g = 10.1 recharge. In the Yellow River alluvial plain, the range of (Yu 2005), and tt is the residence time of groundwater. groundwater age is from 7 to 15 years in the south, the

123 Environ Earth Sci (2013) 69:2037–2057 2051

Fig. 6 The reconstructed tritium values from 1953 to 1985 in the Yinchuan station with a plot of observation data from 1986

Fig. 7 Spatial distribution of the groundwater tritium age Fig. 8 Spatial distribution of the groundwater renewal rates youngest zone in the study area. In the north, the range of K is the radioactive constant (3H = 0.05626/a), i is the groundwater age is 40–55 years. time (a), and A0 = 10 TU. The recovery of tritium concentrations was selected as Groundwater renewal rates the input function. According to the meteorological data of the Yinchuan station since 1952, rainfall of 103.9 mm in Leduc et al. (1996) and Le Gal La Salle et al. (2001) 1980 was selected as a limit (Yu 2005). The groundwater proposed the use of radioisotopes to estimate the ground- renewal rates are showed in Fig. 8. The groundwater water average renewal rate. The main principle is as renewal rates nearly have the same trends as the ground- follows: water tritium age. Overall, the groundwater renewal rates are higher in the south of the Yellow River alluvial plain A ¼ð1 R ÞA ek þ R A ð2Þ gwi ri gwi1 Ri 0i than in the north and are higher in the Yellow River allu- where Rr is the renewal rates, Ag is the content of tritium in vial plain than in the Helan mountain pluvial plain. In the groundwater, A0 is the content of tritium in the input water, south of the Yellow River alluvial plain, the groundwater

123 2052 Environ Earth Sci (2013) 69:2037–2057 renewal rates vary from 16 to 50 % a-1. This area has higher values are -64 and -9.4 %, respectively. The isotopic renewal rates, especially in Wuzhong up to 50 % a-1 that is distributions of deuterium, 18O, and tritium age in the much higher than 1 % a-1 in the Helan mountain pluvial profiles are shown in Figs. 9, 10, and 11. In this study, the plain. There are two reasons. The first reason is in Wuzhong hierarchical GFS in the Yinchuan plain are classified as farmlands are irrigated using water from the Yellow River, the LFSs and RFS (Fig. 9). The LFSs are characterized by and the irrigation return water makes groundwater younger; short flow paths, fast flow velocity, and short average the second reason is the exploitation of groundwater accel- residence time. The RFS is characterized by long flow path, erates the flow of groundwater and increases the groundwater slow flow velocity, and long average residence time. The renewal rates. In the north of the Yellow River alluvial plain, RFS is controlled by regional topography. the groundwater renewal rates decrease from 6 to 1 % a-1, especially in Pingluo where it is less than 1 % a-1. This area Isotopic characteristics as indicators of groundwater has low renewal rates due to the bad groundwater drainage recharge and discharge conditions. According to Yu (2005), the range of the groundwater hydraulic gradient is only 0.3–0.1 %, ground- The distribution of d18O (Fig. 12) can be used to study water flows slowly. Therefore, the groundwater renewal rates groundwater recharge and discharge (Yin et al. 2011b). in this area are consistent with the groundwater renewal Taking -10 % as the lower limit, d18O values are less than ability. In the Helan mountain pluvial plain, the groundwater -10 % in the west of Yinchuan and Pingluo. Groundwater renewal rates are less than 1 % a-1 in the middle caused by recharge mostly comes from the lateral flow. In the east and less groundwater recharge. In the north, the groundwater west sides of the Yinchuan city and in the west of Pingluo, renewal rates are 6 % a-1 that are higher than in the middle d18O values are low. This is caused by the exploitation of due to groundwater mining. In the groundwater abstraction groundwater. In the south of the Yinchuan city, the range of area, the groundwater renewal rates are up to 22 % a-1. The d18O values is from -8to-9.5 %, between the average groundwater level decreases in a rate of 0.2 to 1.3 m/a Yellow River water value (-10.5 %) and the weighted (Yu 2005), indicating that the groundwater exploitation average rainfall value (Fig. 13). It indicates that groundwater rate exceeds the groundwater renewal rates. Therefore, the recharge is mainly from the Yellow River and precipitation. renewal rates (22 % a-1) cannot represent the groundwater In Wuzhong, the heavy exploitation of groundwater is renewal ability in this area, and it is just an indicator of favorable to the Yellow River water recharge. In Lingwu, the groundwater flow conditions. range of d18O values is from -8.5 to -8.6 %. This indicates, in addition to the Yellow River water and atmospheric The distribution of deuterium, 18O, and tritium age precipitation, there are other recharge sources. That is the in the profiles leakage of the confined water from the lower part and the lateral flow from the eastern tableland. The deuterium and 18O values vary from -55 to -73 % The results of stable isotopes are plotted in Fig. 13. The and -7.9 to -10.7 %, respectively, and the average values of d18O and dD in precipitation are used to define

Fig. 9 The distribution of the groundwater tritium age

123 Environ Earth Sci (2013) 69:2037–2057 2053

Fig. 10 The distribution of the groundwater d18O value

Fig. 11 The distribution of the groundwater deuterium value

the local meteoric water line (LMWL). Values of d18O and is strongly affected by evaporation. Therefore, discharge to dD in groundwater scatter around the local meteoric water surface water is one way of groundwater discharge. line and are concentrated in the lower right side of the local meteoric water line, which indicates the impact of signifi- Hydrochemical characteristics as indicators cant evaporation. This phenomenon is very common in arid of groundwater recharge and discharge and semiarid areas (Allison 1983). The surface water (lake) has d18O values in the range of -0.8 to -7.9 %, dD values Groundwater in the Yinchuan plain flows from west to east, from -9to-61 %, and tritium values from 0.5 to 23 TU from south to north. Along the direction of the groundwater 18 2- - ? 2? (Table 1). Most values of d O and dD of surface water are flow, SO4 ,Cl ,Na , and Mg contents are gradually higher than the weighted mean rainfall value and values of elevated (Fig. 14). The hydrochemical type changes from groundwater, and are mostly under the local meteoric water HCO3–SO4–Na–Ca to Cl–SO4–Na–Ca. This infers that the line, indicating the strong evaporation. The intersection of continental salinization and evaporation gradually increase the surface water line and the local meteoric water line during the flow direction. In the north of the plain, the TDS locates between the weighted mean rainfall value and of groundwater is high and Cl-,Na?, and Mg2? are enri- values of groundwater, indicating the surface water ched. This further confirms the lack of the regional receives recharge from precipitation and groundwater, and groundwater flow. Evaporation is the main way of

123 2054 Environ Earth Sci (2013) 69:2037–2057

groundwater discharge in the north of the plain (Shen 1993; Wang et al. 1995). In the Helan mountain pluvial fan, the hydrochemical types of groundwater are different in the south, middle, and north (Fig. 5). In the south, the main groundwater recharge sources are the bedrock ﬁssure water of the Ordovician. The range of the TDS is from 0.42 to 2.44 g/l, and the

hydrochemical type is Cl–SO4–Na–Mg. In the middle, the groundwater hydrochemical type is mainly HCO3–Cl–Ca– Na, similar to the type of spring water. This indicates that the source of groundwater recharge is the bedrock ﬁssure water of the Helan mountain. In the north, the groundwater

hydrochemical type is SO4–HCO3–Ca–Na. Groundwater is recharged by the bedrock ﬁssure water of the Carbonifer- ous and Permian that occurs in the northern Helan moun- 2- tain with higher SO4 contents. In the south of the Yellow River alluvial plain, the

groundwater hydrochemical type is HCO3-SO4–Ca–Mg. The range of the TDS is from 1–2 g/l. This indicates that the source of groundwater recharge mainly is the Yellow

River water (0.5 g/l, and HCO3–SO4–Na–Ca type). Irri- gation using the Yellow River water changes the hydrochemical types. A large amount of the Yellow River water that is of low mineralization and high carbonate contents inﬁltrates groundwater. The Yellow River water dilutes the original water. In the middle of the Yellow River alluvial plain (the Fig. 12 Spatial distribution of the groundwater d18O vaule Yinchuan city), the groundwater hydrochemical type is mul- tiple. In the irrigated area, the groundwater hydrochemical

type is HCO3–SO4–Ca–Mg with TDS less than 1 g/l. In the surrounding area of the Yinchuan city, hydrochemical

types are SO4–HCO3–Ca–Na and HCO3–Cl–Mg–Na. So the sources of groundwater recharges are irrigation return water and the lateral ﬂow from the Helan mountain pluvial fan. The northern part of the Yellow River alluvial plain is the groundwater discharge area.

Conclusions

The hydrochemical and isotopic investigations were con- ducted in the Yinchuan plain to understand the groundwater recharge and discharge. The main conclusions are as follows:

Groundwater in the recharge area is of HCO3–Mg type with low TDS, changes to SO4–Cl–Na–Mg or Cl–SO4–Na– Mg type with TDS ranging from 1–3 g/l along the groundwater ﬂow direction, and ﬁnally becomes Cl–Na type with TDS higher than 3 g/l. According to groundwater age and renewal rates, it shows that the groundwater renewal rates have the similar Fig. 13 Plot of dD and d18O for groundwater from the shallow trend to groundwater age. Overall, it is higher in the south Quaternary aquifer system of the Yinchuan plain of the Yellow River alluvial plain than in the north, and it is 123 Environ Earth Sci (2013) 69:2037–2057 2055

2- 2+ (a)TDS (g/l) (b) SO4 (mg/l) (c) Ca (mg/l)

(d) Cl-2+2+ (mg/l) (e) Na (mg/l) (f) Mg (mg/l)

Fig. 14 Contours of TDS and major ions in the Yinchuan plain

123 2056 Environ Earth Sci (2013) 69:2037–2057 higher in the alluvial plain than in the Helan mountain Hem JD (1989) Study and interpretation of the chemical character- pluvial plain. Groundwater in the south of the Yellow River istics of natural water (3rd edn) US Geological Survey of Water Supply, Paper 2254. USGS, Washington, DC alluvial plain has lower TDS and higher tritium. The value LaBolle EM, Fogg GE, Eweis JB (2006) Diffusive fractionation of 3H of tritium age is from 6 to 25 years. The range of and 3He in groundwater and its impact on groundwater age groundwater renewal rates is from 11 to 15 % a-1. The estimates. WRR 42:W07202 depth of the water cycle is small. Groundwater in the north Le Gal La Salle C, Marlin C, Leduc C (2001) Renewal rate estimation of groundwater based on radioactive tracers (3H, 14C) in an of the Yellow River alluvial plain has higher TDS and unconfined aquifer in a semi-arid area, Iullemeden Basin, Niger. lower tritium. The range of the tritium age is from 45 to Journal of Hydrology 254:145–156 57 years. The range of the groundwater renewal rates is Leduc C, Taupin GD, Le Gal La Salle C (1996) Estimation de la from 6 to 0.1 % a-1. The depth of the water cycle is large. recharge de la nappe phreatique du Continental Terminal 18 (Niamey, Niger) a partir des teneurs en tritium. C.R. Sci. Paris The dD and d O composition of groundwater and sur- 323:599–605 face water indicates that groundwater discharge includes Lucas LL, Unterweger MP (2000) Comprehensive review and critical evaporation and discharge to surface water. In Lingwu, the evolution of the half-life of tritium. J Res Natl Inst Stand Techno sources of groundwater recharge are irrigation return water, 105(4):541–549 Ma JZ, Wang XS, Edmunds WM (2005) The characteristics of precipitation infiltration, leakage of deep confined water, groundwater resources and their changes under the impacts of and the lateral flow from the eastern tableland. human activity in the arid Northwest China—a case study of the Shiyang River Basin. J Arid Environ 61:277–295 Acknowledgments This study was supported by the National Maloszewski P, Zuber A (1996) Lumped parameter models for the Natural Science Foundation of China (40772157). The authors would interpretation of environmental tracer data. In: Manual on like to thank Dr. Xue Zhongqi and Dr. Yu Yanqing from the Ningxia mathematical models in isotope hydrology. IAEA, Vienna, Institute of Geo-engineering and Reconnaissance for their assistance pp 9–58 in this study. 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