Major Element Chemistry of the Huai River Basin, China ⇑ ⇑ Liang Zhang , Xianfang Song , Jun Xia, Ruiqiang Yuan, Yongyong Zhang, Xin Liu, Dongmei Han

Applied Geochemistry xxx (2010) xxx–xxx

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Applied Geochemistry

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Major element chemistry of the Huai River basin, China ⇑ ⇑ Liang Zhang , Xianfang Song , Jun Xia, Ruiqiang Yuan, Yongyong Zhang, Xin Liu, Dongmei Han

Key Laboratory of Water Cycle and Related Land Surface Processes, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, A11 Datun Road, Chaoyang District, Beijing 100101, China article info abstract

Article history: The chemistry of major ions (Ca, Mg, Na, K, HCO3,SO4, Cl and Si) in the water of the Huai River basin was Received 28 January 2010 studied, based on samples from 52 sites from nine different water bodies in July 2008. Ions and total dis- Accepted 3 December 2010 solved solids (TDS) displayed clear spatial patterns with lower concentrations in the south and higher in Available online xxxx the north of the basin; the same conditions were also found in the East Line of South–North Water Transfer Editorial handling by M. Kersten Project (SNWTP) in this region. The Huai River main channel and Hongze Lake have moderate ion concentrations relative to the whole basin. TDS concentrations versus the weight ratios of Na/(Na + Ca) and ternary ions demonstrate that the southern rivers (Shi R. and Pi R.) are mainly controlled by the weathering of carbonates, whereas the northern water systems (Guo R., Shaying R., Nansi Lake and its tributaries) are dominated by the weathering of evaporites. The Huai River main channel, Hongze Lake and the East Line of SNWTP are synergistically inﬂuenced by weathering of evaporites and carbonates, yet Hongze Lake and the East Line of SNWTP are mainly controlled by evaporation and crystallization processes. This study also conﬁrmed that the Huai River is the geographic division between southern and northern China. Most rivers of this basin have very high ionic composition relative to the global median and other world rivers. The spatial patterns and ionic composition also suggest that intensive anthropogenic activities in northern areas of this basin are well characterized. A comparison with WHO and Chinese standards for drinking water indicates that the northern water systems of this basin are not suitable for use as drinking water sources, and pollution control should be improved and enhanced in northern areas of the basin. Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.

1. Introduction 1982; Li and Zhang, 2005; Zhang et al., 1990, 1995; Chen et al., 2005), and the Pearl River (Chen and He, 1999; Zhang, 2000). How- The major chemical composition of river water (e.g., Ca, Mg, Na, ever, few studies have focused on the Huai River, one of China’s ﬁve

K, HCO3,SO4, Cl and Si) can reveal the nature of weathering, largest rivers and the geographic division between southern and patterns and linkages between evaporation and anthropogenic northern China. Until now, only one study (Cheng et al., 2005) processes on a basin-wide scale (Gibbs, 1970; Meybeck, 1987, has reported on water chemistry within the Huai River basin prior 2003; Degens et al., 1991; Brennan and Lowenstein, 2002). Quan- to 2000, and this did not provide detailed data of major-ion chem- tifying the major-ion composition of river water also has broad istry. Thus, this represents a signiﬁcant gap in the understanding of implications, e.g. water quality type, hydrogeology characteristics, river chemistry, physical and chemical weathering, and elemental weathering processes and rainfall chemistry (Brennan and cycles at national and global scales.

Lowenstein, 2002; Cruz and Amaral, 2004). Many previous studies In this study, the major ionic composition (Ca, Mg, Na, K, HCO3, have revealed the major-ion chemistry of the world’s rivers, e.g. SO4, Cl and Si), pH, conductivity (EC) and TDS, of 52 sites were the Amazon (Gibbs, 1972; Stallard and Edmond, 1983, 1987), the determined for the rivers, lakes and artiﬁcial waterways in the Orinoco (Nemeth et al., 1982), the Yangtze River (Chen et al., Huai River basin. In addition, spatial patterns indicative of their 2002), the Yellow River (Zhang et al., 1995; Chen et al., 2005) source were investigated, and the control mechanisms of ion and the Ganges–Brahmaputra (Sarin et al., 1989) amongst others. chemistry in different water bodies of the Huai River basin. For Chinese rivers, most researchers have historically focused on the Yangtze River (Hu et al., 1982; Zhang et al., 1990; Chen 2. Methodology et al., 2002; Li and Zhang, 2005), the Yellow River (Hu et al., 2.1. Huai River basin

⇑ Corresponding authors. Tel.: +86 10 64889814; fax: +86 10 64889849. E-mail addresses: [email protected] (L. Zhang), [email protected] (X. The Huai River is situated between the Yellow River and the Song). Yangtze River (two of the largest rivers in China), and has a total

Please cite this article in press as: Zhang, L., et al. Major element chemistry of the Huai River basin, China. Appl. Geochem. (2010), doi:10.1016/ j.apgeochem.2010.12.002 2 L. Zhang et al. / Applied Geochemistry xxx (2010) xxx–xxx drainage area of 270,000 km2 (Fig 1). Annual mean discharge of the 2500 3 Huai River Basin is 62 km , which is similar to mean discharge of Bengbu 3 the Yellow River (66 km /a); the mean annual precipitation and 2000 Lutaizi evaporation are 920 mm and 900–1500 mm, respectively, and an- Huaibin /s) nual mean temperature of this basin is 11–16 °C, More than 60% of 3 1500 the annual precipitation falls during the flood season from April to October (Fig. 2). Traditionally, the Huai River serves as the geographic division between southern and northern China, in temper- 1000 ature, precipitation and vegetation distribution. Discharge (m Discharge The terrain of the Huai River basin is generally higher in the 500 west and lower in the east, and landforms consist of mountainous areas, hills, plains and swales, with their proportions of the whole 0 basin being 13%, 19%, 52% and 16%, respectively (Ge et al., 2006). A Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec complete sequence of strata are developed in the Huai River basin Month and include Archaean, Neoproterozoic, Cambrian, Ordovician, Carboniferous, Permian, Tertiary and Quaternary (Shao et al., Fig. 2. Monthly variations in the water discharge of the Huai River main channel at Huaibin, Lutaizi and Bengbu (average for the period 1990–2005; Huaibin, Lutaizi 1989). Gneiss and migmatite are primarily distributed in the and Bengbu are the sampling sites 3, 5, 7, respectively, shown in Fig. 1). northwestern mountains, and schist in the western and southwestern mountainous areas; carbonates and petroliferous formations of 2008. Although each site was sampled only once, the range of are widespread in the northern, central and eastern sections; sampling locations provided a comprehensive snapshot for water unconsolidated sediments of Tertiary and Quaternary are distrib- chemistry of the whole basin. uted over the large plains. The East Line of the South–North Water At each site, water samples from the surface, middle and bot- Transfer Project (SNWTP), which is a strategically significant pro- tom of the river/lake were mixed together and then filtered ject to supply water to the North China Plain including Beijing (0.45 lm Millipore nitrocellulose filter) in the field. A small portion and Tianjing city, also passes through this region (Liu et al., 2005). À À 2À of these samples was stored for measuring Cl ,NO3 , and SO4 , while another portion was acidified with HCl to pH < 2 for Na, K, 2.2. Sampling and analysis Ca, Mg and Si determination. Samples were stored at 4 °C in HDPE bottles. Cleaning of plastic bottles and plastic bags was carried out

Many dams and floodgates have been constructed in this region by soaking in 15% (v/v) HNO3 for 24 h and then rinsing with Milli- and are used to store water in the winter and sluice in the summer pore water. (Zhang et al., 2009). Thus, water in the summer is more represen- Electrical conductivity (EC), pH, and total dissolved solids (TDS) tative of the flowing conditions of the water system (Fig. 2). There- were measured in situ using an EC/pH meter (WM22EP, Japan), À fore, the summer season chosen for sampling, and the samples which was previously calibrated. The HCO3 was determined by were collected from 52 sites of the Huai River basin (Fig. 1) in July titration with HCl on the day of sampling before filtration,

N N 0

43 42 Yellow River 45 46 48 TDS concentration:

N36 49 East Line of < 200 mg/L 0 44 47 200 - 400 mg/L 35 SNWTP 50 51 400 - 600 mg/L 52 Nansi Lake 600 - 800 mg/L 41 30 40 > 800 mg/L

N 23 25 0 24 31 39 38 22 26 Guo R. 16 32 37 27 12 9 15 36 33 14 Shaying R. 7 10 8 13 35 N34 28 11 0 6 Hongze Lake

33 29 1 4 5 34 2 3 21 Huai River 18 Shi R. 19 Yangtze River 17 Pi R. N

0 19 32

0 200 400km Shanghai

1120E 1140E 1160E 1180E 1200E 1220E

Fig. 1. Sampling sites in the Huai River basin and spatial distribution of the TDS concentrations.

Please cite this article in press as: Zhang, L., et al. Major element chemistry of the Huai River basin, China. Appl. Geochem. (2010), doi:10.1016/ j.apgeochem.2010.12.002 L. Zhang et al. / Applied Geochemistry xxx (2010) xxx–xxx 3 end-point titration was used with the ﬁnal pH being 4.5. Cations 3. Results (Na+,K+,Ca2+ and Mg2+) and Si were determined using Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) (Thermo Major-ion compositions are given in Table 1. The pH values var- À À 2À IRIS Intrepid II XSP, USA), and anions (Cl ,NO3 and SO4 ) were ied from 6.08 to 7.84, and most sites were characterized as slightly measured using a Shimadzu Ion Chromatograph (IC) meter alkaline with low EC values, varying from 5.5 to 127.8 ls/cm (Table (Shimadzu HIC-SP, Japan). Reagent and procedural blanks were 1). All cations and anions on a basin-wide scale displayed clear determined in parallel to the sample treatment using identical spatial differences, with higher concentrations in the north and procedures. Each calibration curve was evaluated by analyses of lower concentrations in the southern water systems (Fig. 1). quality control standards before, during and after the analyses of Average TDS concentrations of Shi R. and Pi R. are 137.9 mg/L a set of samples. The analytical precision was within 100%, 98.7% and 102.6 mg/L, respectively, whereas TDS in Guo R., Shaying for Na+, 99.5% for K+, 97.6% for Ca2+, 98.9% for Mg2+ and 99.2% for R., Nansi Lake and its tributaries reach up to 919.7 mg/L, 2À À À Si using ICP-AES, 99.4% for SO4 , 98.9% for Cl , 98.6% for NO3 , using 649.6 mg/L, 748.4 mg/L and 956.3 mg/L, respectively. TDS concen- À IC, and 98.0% for HCO3 , respectively. trations at sites in the East Line of SNWTP were higher in the six

Table 1 Hydrochemical compositions of the Huai River basin, China (units mg/L, except EC ls/cm and pH).

Water system Sampling site pH EC Ca Mg Na K HCOÀ 2À ClÀ NOÀ SiO TDS 3 SO4 3 2 Huai River main channel 1 Minggang 6.8 12.9 18.8 10.4 43.6 3.3 100.8 24.5 35.5 0.0 5.4 242.3 2 Xixian 7.0 11.3 16.6 7.7 24.4 3.5 80.0 24.5 20.1 0.0 7.7 184.5 3 Huaibin 7.6 8.2 16.6 7.3 13.8 3.4 68.2 19.6 10.7 0.5 7.3 147.4 4 Nanzhao 7.5 8.5 25.2 8.2 12.4 3.3 62.2 18.6 10.2 2.6 9.4 152.1 5 Lutaizi 7.5 9.6 25.7 8.9 17.1 3.4 86.0 21.9 16.2 5.5 8.7 193.3 6 Huainan 7.5 9.9 27.1 8.9 16.6 3.3 73.1 20.3 15.1 3.4 9.3 177.2 7 Bengbu 7.4 17.5 35.1 12.2 30.8 4.5 134.4 35.9 28.0 5.5 9.8 296.0 8 Linhuaiguan 7.3 15.4 32.6 11.1 26.2 4.1 126.5 29.4 23.5 4.6 9.1 267.2 9 Wuhe 6.1 11.4 32.2 10.6 26.9 3.8 61.3 29.0 24.0 4.9 9.2 201.8 10 Xuyu 7.4 15.8 46.8 14.4 36.7 4.9 71.1 50.9 41.9 5.8 8.1 280.5 Hongze Lake 11 Lihewa 7.0 24.1 51.0 34.6 51.8 9.8 144.0 63.0 46.3 8.8 7.8 417.2 12 Laozishan 7.4 24.0 42.4 15.0 47.2 5.8 146.2 62.5 66.6 20.0 8.7 414.4 13 Jinhu 7.4 20.8 40.8 15.2 42.9 5.5 138.3 47.7 40.9 7.2 8.5 347.0 14 Erheza 7.5 26.2 35.4 20.1 56.5 6.0 154.1 68.0 49.7 2.2 6.0 398.1 15 Sanheza 7.4 16.9 35.9 11.5 29.3 4.3 110.7 37.6 29.2 8.5 8.0 274.9 16 Chenzihu 7.6 48.6 29.5 20.5 46.9 7.6 116.6 48.4 45.4 2.7 7.9 325.6 Shi River 17 Yeji 7.6 6.9 16.4 4.5 7.0 2.3 51.4 14.6 6.7 2.4 10.5 115.8 18 Shangshiqiao 7.5 9.4 23.7 7.5 9.7 2.9 79.0 17.5 7.8 4.7 7.1 160.0 Pi River 19 Hengpaitou 7.7 5.5 13.9 3.4 5.3 2.2 47.4 14.9 5.0 2.7 9.5 104.1 20 Matou 7.6 6.0 13.7 3.7 5.8 2.3 39.5 14.2 6.0 3.9 9.2 98.5 21 Zhengyang 7.6 6.4 14.2 4.1 6.5 2.5 43.5 14.3 7.9 3.4 8.8 105.2 Shaying River 22 Pingdingshan 7.7 18.1 49.0 13.2 112.6 2.6 142.3 55.9 19.2 4.9 8.2 408.0 23 Luohe 7.8 41.3 23.5 14.4 148.0 4.9 135.6 103.5 205.1 1.5 1.2 637.7 24 Huahang 7.5 31.9 54.4 27.5 100.5 7.4 197.6 93.3 72.3 0.8 3.6 557.3 25 Huangqiao 7.4 42.1 22.3 33.7 110.6 9.6 201.6 129.5 109.7 0.0 2.3 619.1 26 Zhoukou 7.6 56.7 51.0 21.9 191.5 6.7 209.3 124.9 266.8 8.8 5.2 886.1 27 Jieshou 7.4 43.5 69.7 25.2 111.6 7.1 217.4 110.3 131.5 21.3 10.7 704.6 28 Fuyang 7.4 93.7 73.0 30.3 123.8 8.3 181.8 128.6 126.8 5.5 10.1 688.2 29 Yingshang 7.4 43.5 61.0 28.0 127.4 8.7 249.0 105.8 93.0 14.7 8.1 695.8 Guo River 30 Taikang 7.5 45.8 44.9 30.4 149.3 14.6 320.1 177.3 94.8 33.8 15.5 880.6 31 Bozhou 7.3 127.8 70.6 39.8 191.5 12.0 202.8 243.6 184.9 36.2 0.3 981.8 32 Mengcheng 7.6 67.6 65.4 42.7 185.6 9.0 355.7 169.4 159.3 16.9 9.1 1013.2 33 Huaiyuan 7.6 50.7 49.8 34.2 176.7 7.5 237.1 160.2 114.3 17.7 5.6 803.2 East Line of SNWTP 34 Jiangdu 7.3 18.7 38.5 11.0 26.5 4.4 112.6 41.2 31.4 7.4 6.6 279.5 35 Gaoyou 7.4 18.9 38.3 11.9 30.7 4.5 122.5 41.5 32.1 6.0 8.1 295.5 36 Baoyin 7.3 19.1 36.5 11.9 31.5 4.7 118.6 40.9 32.8 4.5 8.7 290.1 37 Huai’an 7.4 25.1 42.1 14.6 54.1 4.9 146.2 52.7 51.7 8.4 7.3 382.1 38 Siyang 6.8 32.8 71.5 23.9 65.7 6.6 134.4 116.6 81.7 12.9 7.0 520.3 39 Suqian 6.9 36.7 69.8 23.9 69.9 7.2 146.2 126.9 82.1 8.3 6.9 541.2 40 Pizhou 6.8 40.5 94.1 25.5 72.3 7.8 73.1 153.9 81.7 69.7 15.0 593.1 41 Tai’e’zhuang 7.4 46.2 64.0 29.2 109.1 7.0 85.0 200.2 102.8 7.3 6.1 610.7 42 Jining 7.4 74.3 93.3 43.8 202.5 9.5 150.2 373.8 180.4 7.4 5.7 1066.6 43 Liangshan 7.2 25.2 51.6 15.5 50.9 14.8 132.4 185.0 47.3 17.1 8.3 522.9 Tributaries of Nansi Lake 44 Jishu 7.5 67.6 46.2 38.4 219.4 14.7 296.4 180.6 184.2 18.7 6.6 1005.1 45 Sunzhuang 7.5 54.8 65.7 49.4 180.4 8.6 140.3 259.9 175.7 11.0 9.1 900.1 46 Liangshanza 7.3 78.3 46.8 44.7 237.8 11.3 229.2 302.9 211.5 21.6 5.6 1111.4 47 Yanzhou 7.4 59.8 74.1 33.9 184.7 9.2 146.2 178.2 155.7 15.1 11.4 808.6 Nansi Lake 48 Weishandao 7.5 46.9 61.8 33.3 134.2 8.6 173.9 206.4 120.6 0.0 5.5 744.3 49 Erjibashang 7.5 56.1 51.9 37.1 166.4 8.1 183.8 220.4 150.9 5.1 5.4 829.0 50 Erjibaxia 7.6 55.3 51.6 35.3 157.9 8.0 195.6 223.1 147.0 6.3 5.5 830.3 51 Dushandao 7.4 42.1 58.2 21.6 97.8 11.3 152.2 132.2 104.8 6.7 9.7 594.5 52 Nanyanghu 7.4 52.7 55.4 33.9 161.8 9.1 90.9 241.0 146.4 0.0 5.2 743.7 Mean 7.4 35.2 45.0 21.5 87.3 6.7 142.6 106.9 81.4 9.5 7.7 508.6

TDS equal to sum of major ions plus SiO2.

Please cite this article in press as: Zhang, L., et al. Major element chemistry of the Huai River basin, China. Appl. Geochem. (2010), doi:10.1016/ j.apgeochem.2010.12.002 4 L. Zhang et al. / Applied Geochemistry xxx (2010) xxx–xxx

Table 2 Pearson correlation matrix for major ions and pH, EC and TDS of the upper Huai River basin.

pH EC Ca Mg Na K HCO3 SO4 Cl NO3 Si TDS pH 1 EC 0.09 1 Ca À0.19 0.65** 1 Mg 0.02 0.84** 0.69** 1 Na 0.15 0.84** 0.62** 0.89** 1 K À0.04 0.71** 0.59** 0.76** 0.74** 1 ** ** ** ** ** HCO3 0.15 0.53 0.41 0.68 0.71 0.67 1 ** ** ** ** ** ** SO4 À0.01 0.77 0.72 0.89 0.87 0.78 0.50 1 Cl 0.14 0.84** 0.56** 0.82** 0.92** 0.64** 0.60** 0.79** 1 ** ** ** * ** * * NO3 À0.24 0.39 0.55 0.32 0.29 0.46 0.23 0.35 0.27 1 Si À0.13 À0.35* 0.06 À0.29* À0.33* À0.08 À0.05 À0.24 À0.42* 0.38* 1 TDS 0.08 0.84** 0.71** 0.93** 0.97** 0.82** 0.77** 0.91** 0.91** 0.39** À0.24 1

* Correlation is signiﬁcant at the 0.05 level. ** Correlation is signiﬁcant at the 0.01 level.

+ 2+ À 2À Na ,Ca , HCO3 and SO4 . Sodium and Ca comprise 76.5–83.6% Tributaries of NansiLake of total cations, while the sum of HCOÀ and SO2À account for NansiLake 3 4 GuoR. 66.4–88.2% of anions (Fig. 3). East line of Yellow R. ShayingR. SNWTP HongzeLake 4. Discussion Yangtze R. Ganges HuaiRiver main channel 4.1. Spatial pattern of major ions Pearl R. St. Lawrence Shi R. Pi R. Significant spatial variations of major ions could reflect the Amazon influence of different lithologies and anthropogenic activities

TDS (mg/L) Global Median (Chen et al., 2002). In the present study, the southern water has a lower EC value and lower concentrations of hydrochemical Zaire variables. This coincides with the southern rivers (Pi River and Orinoco Shi River) and the Huai River main channel, that originates from southern and southwestern mountainous areas, where gneiss, migmatites and schist are very common, and there is little anthropogenic activity (Ge et al., 2006). In contrast, the northern water Na/Na+Ca has high concentrations of ions. This results mainly from the unconsolidated sediments of strata development on the wide Fig. 3. The Gibbs graph of different water bodies in the Huai River basin and other world rivers. northern plains (Liu, 1999) and intensive industrial–agricultural activity (Cheng et al., 2005; Zhang and Shan, 2008). northern sites (avg. = 642.5 mg/L) and lower in the four southern sites (avg. = 311.8 mg/L). In the whole basin, the Huai River main 4.1.1. Comparison with Yangtze River and Yellow River channel and Hongze Lake have moderate TDS values, varying from Within a similar longitude gradient to the Huai River basin, the 152.1 to 417.2 mg/L, and the lowest (98.5 mg/L) and highest stations in the Yangtze River basin (from Wuhanguan to Shanghai) (1111.4 mg/L) TDS values were displayed in the Pi River (Site 20) have TDS concentrations ranging from 75 mg/L to 225 mg/L (Chen and one tributary of Nansi Lake (Site 46), respectively. et al., 2002); for stations in the Yellow River basin (from Hua- Sodium and Ca are the most abundant cations with concentra- yuankou to Lijin), however, TDS values were 291–521 mg/L (Chen tions of 5.3–237.8 mg/L and 13.7–45.0 mg/L, respectively (Table 1). et al., 2005), but the two sides (northern and southern) of the Yan- Potassium is the least abundant major cation with an average con- gtze and Yellow Rivers did not show such a large difference com- tent of 2.2–14.8 mg/L. Bicarbonate is the most abundant anion, and pared to the Huai River. Together with the ions results of the its concentration ranges from 39.5 to 355.7 mg/L, and the values of present study, it shows that the Huai River is the natural ‘‘bound- 2À ary’’ between the Yangtze River basin and the Yellow River basin, SO4 , the second most abundant anion, varied from 14.2 to À and this also confirms that the Huai River is the geographic divi- 373.8 mg/L, NO3 is the least abundant anion for all sites with average concentrations of 3.29–16.61 mg/L. Silicon has a constant low sion between southern and northern China. concentration in the different water bodies of the whole Huai River The average TDS concentration in the Huai River main channel basin, and its average concentration varied from 6.17 to 9.63 mg/L. is similar to that of the Yangtze River and the Ganges (Table 3), but Relationships between ions, EC and TDS were examined for all is more than seven times the global median of 65 mg/L (Meybeck sampling sites (Table 2). All cations and anions have significant po- and Helmer, 1989; Meybeck, 2003). The high average TDS value sitive correlations (p < 0.05) with each other with the exception of (508.6 mg/L) of the whole basin is close to that of the Yellow River. À À This is mainly attributable to the fact that the northern plains of one relationship, Cl and NO3 . There are no significant correlations À 2À the Huai River basin have homologous geomorphic structures between Si and Ca, K, HCO3 and SO4 . Both EC and TDS have a strong positive correlation (p < 0.01) with all cations and anions. and soil compositions with the Yellow River plain (Shao et al., Sodium (the most abundant cation) and Ca (the second most 1989; Liu, 1999). abundant cation) contribute 22.6–69.8% and 13.7–56.2%, respec- 2À tively, to the major cation budget. Bicarbonate and SO4 account 4.1.2. Spatial pattern of the East Line of SNWTP for 23.9–70.8% and 17.4–44.3%, respectively, of total anions. There- Water of the East Line of SNWTP will be pumped from the fore, the water composition of the whole basin is dominated by pumping stations near Yangzhou in the lower reaches of the

Table 3 Major-ion concentrations in the present study and with other rivers from the literature.

River Ca Mg Na K HCO3 SO4 Cl NO3 SiO2 TDS References Huai River basin 45.0 21.5 87.3 6.7 142.6 106.9 81.4 9.5 7.7 508.6 This study (average of basin) Huai River 27.7 10.0 24.8 3.7 86.4 27.5 22.5 3.3 8.4 214.2 This study (main channel) Yangtze River 34.1 7.6 8.2 0.1 133.8 11.7 2.9 2.9 205.9 Chen et al. (2002) Yellow River 44.9 22.4 60.0 3.5 200.1 83.2 46.9 7.4 18.0 486.4 Zhang et al. (1995) Pearl River 38.4 4.5 2.1 0.1 132.0 7.7 1.2 6.0 192.0 Chen and He (1999) Amazon 12.0 1.7 3.9 1.2 43.9 4.0 3.9 0.6 9.0 80.3 Stallard and Edmond (1983) Orinoco 2.8 0.5 1.4 0.8 6.7 2.4 8.9 3.0 26.4 Nemeth et al. (1982) St. Lawrence 28.9 6.8 10.4 1.6 84.2 20.0 20.9 2.4 175.1 Tremblay and Rivard (1985) Ganges 25.3 7.0 10.1 2.7 126.9 7.2 5.0 8.4 192.6 Sarin et al. (1989) Zaire 2.0 1.2 1.4 1.2 12.2 0.8 1.1 8.4 28.3 Zhang et al. (1995) Global Median 8.0 2.4 4.7 0.1 30.5 4.9 3.9 1.0 9.5 65.0 Meybeck and Helmer (1989)

Yangtze River, through the Jing-Hang Grand Canal and its parallel 4.2.2. Weathering river channels across the North China Plain (Fig. 1). Because the Gibbs (1970) suggested that a simple plot of TDS versus the highest place on the East Line of SNWTP is about 40 m higher than weight ratio of Na/(Na + Ca) or Cl/(Cl + HCO3) could provide infor- the water level of the Yangtze River, the project needs 75 pumping mation on the relative importance of three major-natural mecha- stations in 13 cascades. About 90% of the East Line of SNWTP canals nisms controlling surface water chemistry, which include will use existing river channels or lakes (Liu et al., 2005), some of atmospheric precipitation, evaporation and fractional crystalliza- the water will originate from the Huai River (Hongze Lake) and tion, as well as rock weathering. Nansi Lake, so the water quality of the Huai River basin is very TDS concentrations versus weight ratios of Na/(Na + Ca) for the important for the East Line of SNWTP. Huai River basin and other international rivers have been plotted In this study, the southern 4 sites of the East Line of SNWTP together (Fig. 3). The wide northern areas of the Huai River basin had lower ionic and TDS concentrations than the six northern (Shayin R., Guohe R., Nansi Lake and its tributaries), Hongze Lake, sites, which were homologous with the five sites of Nansi Lake and the east line of SNWTP, as well as the Yellow River in China, (Fig. 1 and Table 1). This is consistent with previous studies are characterized by a high ratio of Na/(Na + Ca) and a high TDS (Liu et al., 2005) and indicates that southern water quality is concentration, suggesting that the surface water of these areas is better than the northern sections. It also shows that the north- typically controlled by evaporation and crystallization processes ern part of the Huai River basin is strongly influenced by indus- (Gibbs, 1970). This is most likely because these areas are part of trial–agricultural activities (Tang et al., 2008). Water pollution an arid or semiarid region (Chen et al., 2005). Also, intensive agri- control and treatment of the northern part of the Huai River cultural activities (Zhang and Shan, 2008), may be responsible basin are necessary for the East Line of SNWTP (Liu et al., since long-term farming practices can increase the weathering 2005; Tang et al., 2008). and erosion of soil and result in a higher TDS (Zhang et al., 1995). A high level of evaporation can also increase the salinity 4.2. Mechanisms controlling the major-ion chemistry of the the Huai and the relative proportion of Na to Ca (Gibbs, 1970). On the other River basin hand, the Shi River and Pi River are characterized by a lower ratio of Na/(Na + Ca) and a lower TDS concentration, closer to that of the River solutes have multiple sources deriving from physical, Yangtze, Ganges and Pearl Rivers, which are typical of rock-domi- chemical and biological processes in the drainage basin. The major nated rivers (Chen et al., 2002; Sarin et al., 1989; Chen and He, sources of dissolved salts in a river include sea salts carried in the 1999). As illustrated in Fig. 3 the Huai River main channel is mod- atmosphere and deposited in the river (cyclic salts); weathering of erately enriched in TDS and plots in the middle of the Gibbs plot, silicate, carbonate, evaporite and sulfide minerals; and anthropo- indicating that it is influenced by evaporation and crystallization genic input. Their origins are discussed below. processes, together with rock weathering. It is well known that weathering of different parent rocks (e.g., 4.2.1. Cyclic salts carbonates, silicates and evaporites) yields different combinations The average residence time of sea salts in the atmosphere is of dissolved cations and anions (Garrels and Mackenzie, 1971; about 3 days (Junge, 1972). As a result, the contribution of cyclic Stumm, 1992). For instance, Na and K are supplied by the weather- salts to riverine dissolved salt loads is expected to decrease with ing of evaporites and silicates, Ca and Mg are supplied by the À À increasing distance from the sea. It has long been known that Cl weathering of carbonates, silicates and evaporites, HCO3 by carbon- 2À À in surface waters with no terrestrial sources of the element de- ates and silicates, SO4 and Cl by evaporites. Silica, on the other clines systematically as a function of increasing distance from hand, is derived exclusively from the weathering of silicates, and the sea (Stallard and Edmond, 1981). In the present study, ClÀ con- weathering of carbonates might contribute to the silica fluxes due centrations in water do not decline with increasing distance from to the dissolution of biogenic silica in carbonates (Jansen et al., the sea, but show obviously higher amounts in the northern water 2010). and lower amounts in the southern water. For instance, ClÀ con- To explore the relative importance of different weathering re- centrations in some sites on the Shaying River and the Guo River gimes, ternary plots of cations (Ca À Na + K À Mg) as well as anions are more than 100 mg/L, but those of the southeastern sites from (HCO3 À Cl + SO4 À SiO2) and silica were constructed (Fig. 4). Sites the Shi River and the Pi River are consistently less than 10 mg/L. in the northern water systems (Guohe R., Shaying R., Nansi Lake Consequently, the ClÀ distribution in the Huai River results mostly and its tributaries) fall in the cluster towards the Na + K apex from anthropogenic sources and/or weathering of evaporites, and and Cl + SO4 apex, indicating that the northern part of the basin sea salt influence on the Huai River basin is relatively small. Similar is dominated by the weathering of evaporites. The southern sites results were also found in the Yangtze River basin and Yellow River of the Shi River and Pi River have high HCO3 contents and fall close basin (Chen et al., 2002, 2005). to Ca apex, suggesting that the weathering of carbonates is

Please cite this article in press as: Zhang, L., et al. Major element chemistry of the Huai River basin, China. Appl. Geochem. (2010), doi:10.1016/ j.apgeochem.2010.12.002 6 L. Zhang et al. / Applied Geochemistry xxx (2010) xxx–xxx

Huai River main channel Shaying River Guo River Shi River Pi River Hongze Lake East Line of SNWTP Tributaries of Nansi Lake Nansi Lake

Fig. 4. Ternary plots showing the relative abundances of cations (Ca À Na + K À Mg) as well as anions (HCO3 À Cl + SO4 À SiO2) and silica for the Huai River basin.

(meq/L) (meq/L) (meq/L) (a) (b) (c)

(meq/L) (meq/L) (meq/L) (meq/L) (meq/L) (meq/L) (d) (e) (f)

(meq/L) (meq/L) (meq/L)

Fig. 5. Proportions of major ions for the water of the Huai River basin (the legends see Fig. 4).

signiﬁcant in these waters. The Huai River main channel, Hongze In addition, most sites fall under the isometric line of HCO3/ Lake and East Line of SNWTP are widely spread in the ternary plots, Cl + SO4 (Fig. 5a), HCO3/Na + K (Fig. 5b), HCO3/Ca + Mg (Fig. 5c), indicating that they are inﬂuenced by weathering of evaporites and indicating that the dominance of evaporite rock weathering carbonates together. Meanwhile, the concentration ratio of and the weathering of carbonates could not explain the whole

HCO3:Cl + SO4:Si is 17.7:58.2:1 (Table 2) in the basin and there is composition of Ca and Mg in the water. The sites fall near the À 2À no signiﬁcant correlation between Si and Ca, K, HCO3 and SO4 two sides of the isometric line of Ca + Mg/Na + K (Fig. 5d), (Table 1), indicating that weathering of evaporites and carbonates Cl + SO4/Na + K (Fig. 5f), Cl + SO4/Ca + Mg (Fig. 5g), also pointing are primary and secondary contributors for the major ions, respec- to the dominance of weathering of evaporite in this region, tively, and silicate-weathering plays a less important role in deter- since sulphates and chlorides are the primary minerals of mining major ions for the whole basin. evaporite.

Table 4 Range in values of geochemical variables in waters and WHO (2006) and Chinese State Standard (CSS) for drinking water (units: mg/L except, EC ls/cm, and pH).

Parameters Huai River basin WHO (2006) CSS Average* Min Max Mean Max desirable Max permissible pH 6.1 7.8 7.4 7.0–8.5 6.2–9.5 EC 5.5 127.8 34.6 750 1500 Hardness 48.4 412.9 198.7 200 500 450 TDS 98.5 1111.4 509.6 600 1000 1000 Ca 13.7 94.1 45.0 75 250 15.0 Mg 3.4 49.4 21.1 30 150 4.1 Na 5.3 237.8 87.5 50 200 200 6.3 K 2.2 14.8 6.7 100 250 2.3 À HCO3 39.5 355.7 142.6 300 600 58.4 2À 14.2 373.8 109.2 250 600 250 11.2 SO4 ClÀ 5.0 266.8 80.5 250 600 250 7.8 À NO3 0.0 69.7 9.3 50 50 50 1.0

* Averages of world rivers (Meybeck and Helmer, 1989).

4.2.3. Anthropogenic causes northern water systems (Guo River, Shaying River, Nansi Lake

Agricultural activities can accelerate the weathering process for and its tributaries) have high TDS values and high Cl + SO4 and rivers (Meybeck and Helmer, 1989; Zhang et al., 1995; Semhi et al., Na concentrations, and are dominated by the weathering of evap- 2000; Chen et al., 2002; Meybeck, 2003; Perrin et al., 2008). Re- orites. The Huai River main channel, Hongze Lake and the East Line ports have suggested that agricultural sources could account for of the SNWTP are influenced by the weathering of evaporites and 70% of the total pollutants during the flood season in the Huai River carbonates, yet Hongze Lake and the East Line of SNWTP are basin (Tang et al., 2008). In this study, the Huai River has been mainly controlled by evaporation and crystallization processes. shown to have much higher ion concentrations than the global Generally, weathering of evaporites and carbonates are the pri- median (Table 3), in common with other Asian rivers (Yangtze R., mary and secondary contributors for the major ions, respectively, Ganges, Yellow R. and Pearl R.). This is mainly attributable to great and silicate-weathering contributes very little to the dissolved ions physical and chemical erosion and intensive agricultural activities in the whole basin. over the Sino-Indian subcontinent (Zhang et al., 1995; Meybeck, Most rivers of the Huai River basin and other Asian rivers have 2003; Perrin et al., 2008). higher ion concentrations than the global median, likely a result of Most northern sites of the Huai River basin have high values for the intensive agricultural activities over the Sino-Indian subconti- cation and anion concentrations (Table 1), especially the sites of nent. Spatial variations in the Huai River basin indicate that the the Guo River and Nansi Lake and its tributaries, with unusually anthropogenic impacts are different in southern and northern + 2+ 2À À + 2+ 2À À high Na ,Ca ,SO4 and Cl concentrations, even higher than in water systems, and the unusually high Na ,Ca ,SO4 and Cl con- the Yellow River (Tables 1 and 4), whose basin has more than a centrations of northern waters also reflect the intensive industrial 5 ka history of agricultural activities (Zhang et al., 1995). This also activities in the north of the Huai River basin. Ion compositions of indicates that industrial activities (e.g. major utilization of sulphate southern water systems are within the safe limits for drinking and chloride minerals) intensively influence the northern water water standards, but northern water systems of the Huai River ba- systems of the Huai River basin (Wang and Ongley, 2004; Cheng sin are not suitable for use as drinking water sources. Pollution et al., 2005). control should be improved and enhanced in the northern area with the construction of SNWTP. 4.3. Quality assessment Acknowledgments Southern water systems have low mineralization with low hardness, and northern water systems have high values (Table 1, This study was supported by the Key Program National Natural Fig 1). By comparison with the World Health Organization (WHO, Sciences Foundation of China (Grant No. 40830636), China 2006) and Chinese State Standards (CSS) (Chinese Ministry of Postdoctoral Science Foundation (Grant No. 20090450564), key Health, 2006) for drinking water (Table 4, most northern variables Project of the Natural Science Foundation of China (Grant No. are over the maximum desirable limits and some of them exceed 40721140020), and the project of The Ministry of Science and the maximum permissible values of WHO and CSS standards. It Technology of China (Grant No. 2008ZX07010-006-1). 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