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Chemie der Erde 73 (2013) 343– 356

Contents lists available at ScienceDirect

Chemie der Erde

jou rn al homepage: www.elsev ier .de /chemer

ydrochemical characteristics and controlling factors for waters’hemical composition in the Tarim Basin, Western China

ing Boa,b, Chenglin Liua,b,∗, Pengcheng Jiaoa, Yongzhi Chena, Yangtong Caoa

MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, 100037 Beijing,hinaInstitute of Mineral Resources, Chinese Academy of Geological Sciences, 100037 Beijing, China

r t i c l e i n f o

rticle history:eceived 24 March 2012ccepted 11 June 2013

eywords:ydrochemical typesontrolling factorsackground value

a b s t r a c t

This paper covers the chemical and isotopic composition of river water, groundwater from wells(15–25 m), saline spring water and stagnant surface water providing evidence for controlling factorsof water composition and water evolution process in the Tarim Basin, Xinjiang, western China. Analyticaldata for major and minor ions of totaling 537 water samples were obtained from both years of teamworkand old reference materials. It is found that the ion background value ratio SO4/Cl for river water (2.75)of the Tarim Basin is two times higher than that of the Qaidam Basin (0.88) and 18 times higher thanseawater (0.14); K/Cl of these two basins (0.06 and 0.07) are all two times higher than seawater (0.02).

sotopic compositionsydrothermal Ca–Cl brinesop Nurarim Basin

This reveals that material sources of Lop Nur are relatively richer in potassium and sulfate, while poorerin chloride. Gradual changes of stable isotopic compositions in waters clearly indicate the effect of evap-oration on water evolution of the basin. Besides evaporation and weathering of surrounding rocks, widedistribution of chloride type water, which commonly exist in saline springs/brines and seldom exist inother waters, indicates that hydrothermal Ca–Cl brines discharged from deep within the earth join waterevolution of the basin.

. Introduction

Hydrochemistry is of great importance to researching on watervolution of arid regions. Hydrochemical characteristics such ashemical composition, hydrochemical types and environmentalackground value usually can help to understand the environmen-al and geological conditions in which waters are formed, i.e. theontrolling factors.

In recent years, hydrochemical researches usually focus onecharge, mobilization, and evolution mechanism of groundwa-er. Shanyengana et al. (2004) studied major-ion chemistry androundwater salinization in ephemeral floodplains in arid regionsf Namibia. Tsujimura et al. (2007) researched stable isotopic andeochemical characteristics of groundwater in a semi-arid region-herlen River Basin in eastern Mongolia. Tweed et al. (2011) studiedecharge and salinization processes of groundwater in the Lakeyre Basin, Australia, through the study of major-ion chemistry,

table isotope composition, etc. Vanderzalm et al. (2011) studiedecharge sources and hydrogeochemical evolution of groundwatern alluvial basins in arid central Australia. In China, groundwater

∗ Corresponding author at: 26 Baiwanzhuang Street, Xicheng District, 100037eijing, China. Tel.: +86 010 68999067; fax: +86 010 68327263.

E-mail address: liuchengl@263.net (C. Liu).

009-2819/$ – see front matter © 2013 Elsevier GmbH. All rights reserved.ttp://dx.doi.org/10.1016/j.chemer.2013.06.003

© 2013 Elsevier GmbH. All rights reserved.

hydrochemistry was studied in many regions, such as the ErdosBasin (Dou et al., 2010), the Longdong Basin (Zhang et al., 2006b; Liuet al., 2009), the Ejin Basin (Zhang et al., 2006a), the Hexi Corridor(Bai and Yang, 2007), the Gongpoquan Basin (Chen et al., 2008), theTarim Basin (Li et al., 1995; Wu and Guo, 2004; Zhu and Yang, 2007;Zeng et al., 2008; Dai et al., 2010) and so on. Besides, salt lakes, salinesprings and their evolution mechanism were also studied in aridzones for sylvite exploration. For instance, in China, the Qinghai-Tibet Plateau (Zheng and Liu, 2009), the Qaidam Basin (lying to thesoutheast of the Tarim Basin) (Fan et al., 2007a,b) and the TarimBasin (Tan et al., 2004; Ma and Ma, 2006) are the main researchareas. As for river water, formal references on river water hydro-chemistry in arid zones in China are relatively fewer (Zhou andDong, 2002; Zhu and Yang, 2007).

Chemical composition and the content of different ions in nat-ural water bodies may be controlled by many factors, such asthe surrounding geology, rock weathering, the climate, rechargesfrom precipitation, surface water or groundwater, so their materialsources and evolution processes are very complicated.

The Tarim basin, as the biggest enclosed inland basin of Chinaand being rich in mineral resources (especially oil, gas and salt

deposits), has caused interests of many scholars. However, fewhydrochemical evidences have been offered for research on its evo-lution process. Old hydrochemical materials can no longer meet thedemand of new research progress in this area.

3 er Erd

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mi

44 Y. Bo et al. / Chemie d

In this research, based on analytical data of 537 natural wateramples obtained from years of teamwork (n = 302, 159 river wateramples, 62 saline spring/brine samples, 31 groundwater samplesnd 50 stagnant surface water samples) and old geochemical resultsn = 235, 34 river water samples, 134 saline spring/brine samples,1 groundwater samples, 16 stagnant surface water samples) (Guo,973; IOD & BGMR, 1977; Chen, 1978; Tan et al., 2004; Ma and Ma,006), hydrochemical composition, hydrochemical types, control-

ing factors of waters in the Tarim Basin, as well as environmentalackground value for river water, are analyzed in order to helpo understand hydrochemical characteristics and evolution mech-nisms of the basin. Besides, oxygen (�18O) and hydrogen (�D)sotopic compositions of 89 water samples are analyzed to offer

ore information for this research.Environmental background value is the content of chemical ele-

ent in relatively clean (less influenced by human activities) areasn studied regions under the present environmental conditions

Fig. 1. Lithologic sketch-map of the Tarim Basin. According to Z

e 73 (2013) 343– 356

(Chen, 2000). In the view of geochemistry, normal content of an ele-ment is called its background content, and its average value is calledthe background value (Tao, 1981). Unusual data rejection is thefirst step for determination of element environmental backgroundvalue (Huang and Xu, 2008). However, most criterions for rejectionof unusual values take data normal distribution as an assumption,therefore there are some limitations in their application (Wei et al.,2009). In this research, boxplot was used in unusual values rejectionfor determination of element environmental background value.

2. Site description

2.1. Physical geography

The Tarim Basin of Xinjiang is a large 500,000 km2 closed basin,located in China’s far west (Fig. 1). It is surrounded by the TianshanMountains to the north, the Pamirs Plateau to the west, the Kunlun

hang (1980), Li et al. (1991), Ma (2001) and Mao (1998).

Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356 345

Table 1Annual runoff volumes of main river systems in the Tarim River Basin (from He, 1998).

River system River name Monitoring station Annual runoff volume (108 m3)

Hotan riverYurungkax river Tongguziluoke 22.23Karakax river Wuluwati 21.63

Yarkant riverYarkant river Kajun 64.33Tiznap river Yuzimenleke 8.17

Aksu riverToxkan river Shaliguilanke 25.76Kumalake river Xiehela 46.04Tailanhe river Tailan 7.35

Weigan river

Muzat river Ahebulong 14.54Kabusilanghe river Kamuluke 27.08Tailewaiqiukehe river TeerweiqikeKalasuhe river Kalasu 2.13Heizihe river Heizi 3.15

MabPN(DtaTcbf

2

brr(aoasGattwSnaw

2

dPNi2oBswa

Kuqa river

Kaidu river, Kongqueriver

Kaidu riverDina river

ountains to the south, the Karakoram Mountains to the southwestnd the Altun Mountains to the southeast. At the east end of theasin lies a saline depression-Lop Nur. Since the Late Pliocene-earlyleistocene, the west of the Tarim Basin has been uplifted, and Lopur has sunk and become the final confluence of waters in the basin

Liu et al., 2002), with an altitude of 780 m. The famous Taklimakanesert (the second biggest desert in the world) dominates much of

he central basin. Between two big mountain systems-the Tianshannd the Kunlun Mountains, there are plains or sub-basins of thearim Basin (Lv, 1993). Being in the warm temperate zone with dryontinental climate, the annual mean temperature of the basin isetween 10 ◦C and 12 ◦C, while annual mean precipitation rangesrom 15 mm to 60 mm (Zhu and Yang, 2007).

.2. Hydrology

As water flows into the basin plain, it includes 144 rivers, whichring meteoric waters from the surrounding mountains. Theseivers belong to nine inland river systems, among which the annualunoff volume of Yarkant River (more than 5 × 109 m3) is the largestTable 1, He, 1998). A second major source of inflow is derived fromctive fault zones-saline springs/brines. Saline spring waters areften exposed around salt domes, two wings of anticlines, gulliesnd valleys, with low flow rate. This can be interpreted as sub-urface brines that have risen to the surface along deep faults.roundwater of the basin usually comes out at the mountain passesnd join into river runoff, with a small part penetrating aside intohe plain groundwater. The annual groundwater inflow volume tohe plain area is 4.455 × 109 m3 (He, 1998), including pore phreaticater and confined water stored in loose Quaternary sediments.

tagnant surface water in the Tarim Basin includes long-term stag-ant surface water (lake water, reservoir water) and pond waternd short-term stagnant surface water (ditch water and puddleater).

.3. Geology

The basin is a big and stable Craton in China, with gypsum-salteposited in the Cambrian system, the carboniferous system, theermian system, the Cretaceous system, the Paleogene system, theeogene system and the Quaternary system (Zheng et al., 2006). It

s a superimposition of several small marine basins (Liu et al., 2006,008). As the sub-basins in the Tarim Basin, the Kuqa Basin (northf the Tarim Basin) and the Shache Basin (southwest of the Tarim

asin) were formed in marine or marine continental evaporationedimentary environment from the Cretaceous to Early Tertiary,ith evaporite deposit layer thickly and widely distributed. In the

lpine zone of the basin, though crystalline rocks like granite and

Lanqian 3.34Dashankou 36.46Dina river 3.41

metamorphic rocks contain high content of Na,K, Ca, etc., they arenot easy to be dissolved, so bicarbonate is the main soluble salt,and partially exist marble and limestone. However, lower mountainzones are composed of salt-bearing rock of the Tertiary, so solublesalts dominate (Zhu and Yang, 2007).

On the basis of geographical (distribution of rivers and moun-tains) and geological conditions, the Tarim Basin is divided intofive regions (Figs. 1 and 2). Region 1 contains the southern andsoutheastern Tarim Basin, i.e. the north of the Kunlun Mountainsand the Altun Mountains, from the Yurungkax River to the east ofthe Milanhe River; Region 2 is the southwestern Tarim Basin, i.e.the north of the Karokoram Mountains, from the Yarkant River tothe Karakax River; Region 3 is western Tarim Basin, including theKashigaer River and the surrounding rivers that originate from thePamirs Plateau; Region 4 is the northern Tarim Basin, i.e. the southof the Tianshan Mountains; central Tarim Basin-hinterland of theTaklimakan desert is Region 5.

Region 1 is dominated by granite which mainly formed inmiddle-late Proterozoic era, Devonian, Carboniferous and Permianperiod; Paleogene (E1–2), Neogene (N1) gypsum or gypsum-bearingrocks exist in few areas. In Region 2, granites are extensivelydeveloped, which were formed during the Yanshanian age, theIndosinian age, the middle-late Proterozoic era and the Permianperiod; late Cretaceous and Paleogene evaporate rocks, includinggypsum and halite, can be seen on the western Kunlun piedmontzone (the Yigeyazi-Aertashi and Pishan-Sangzhu areas) and fewupper Cretaceous and upper Triassic gypsum and gypsum-bearingrocks can be found in marginal zones of the basin; carbonatitesor carbonate-bearing rocks seldom exist in this region. Region 3is characterized by great development of late Cretaceous, Paleo-gene and Neogene evaporate rocks such as gypsum, halite or othergypsum-bearing rocks; few carbonatites only occur in Early Paleo-zoic strata; small amounts of granite can only be seen at the southedge of this region. In region 4, carbonatites occurred in Early Paleo-zoic strata (O1, O1+2) are mainly distributed in Aheqi-Keping area;the Paleogene and Neogene evaporites including halite, gypsumand gypsum-bearing rocks are distributed in Baicheng-Kuqa area,while the granite seldom exist. The Quaternary deposit mostly cov-ers region 5, some Paleogene and Neogene gypsum rocks can onlybe seen between the Yarkant River and the Hotan River.

3. Material and methods

3.1. Sample collection and determination

A total of 302 water samples were collected from the Tarim Basinfrom 2002 to 2010:

346 Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356

F er, sas 998).

•••

•••••

t

glAto(pirsw

tqcastssN(be

ig. 2. Distribution of sampling spots of the Tarim Basin. 1–5 stands for river wattagnant surface water, respectively; base map is according to Li (1991) and Mao (1

46 samples in 2002 (mainly river water),27 in 2003 (river water and stagnant surface water),15 in 2004 (river water, surface stagnant water and salinespring/brine),24 in 2005 (mainly river water and stagnant surface water),35 in 2006 (mainly river water, and few saline spring/brine),86 in 2007 (mainly river water and groundwater),7 in 2008 (saline spring/brine),60 in 2010 (mainly saline spring/brine, groundwater and stagnantsurface water).

Saline spring samples are mainly from the Kuqa Basin-north ofhe Tarim Basin in region 4.

Sampling was done in accordance to the concerned operationuides (MGMR, 1987; EPA, 2004). Groundwater samples were col-ected from wells (the depth range is 15–25 m) of local villages:fter 1–2 h pumping, filtered through 0.45 �m filter paper and

ransferred to two low-density polyethylene bottles. One bottlef sample was for anion analysis and the other for cation analysisacidified with HNO3 at a final concentration of 5%). Water sam-les for oxygen and hydrogen isotope analysis were also collected

n inclosed high-density polyethylene bottles without adding anyeagent. Samples of other water bodies were also processed in theame way. During sampling, pH values for part of these samplesere measured with portable pH meter.

Each batch of samples were sent to the National Research Cen-er for Geoanalysis (NRCGA, PRC) for chemical analysis. Standarduality control methods were used to ensure accuracy in lab pro-esses, according to the guideline DZ/T 0130-2006 (Ministry of Landnd Resources of the People’s Republic of China, 2006). Standardolutions parallel samples and blank samples were used duringhe process of sample analyzing. Besides, 20% of each batch ofamples was rechecked in other certified laboratories with theame method to assure the reliability of analytical results. K+, Ca2+,

a+, Mg2+ were detected according to the guideline JY/T 015-1996

Education Commission of the People’s Republic of China, 1996)y Inductively Coupled Plasma and Atomic Emission Spectrom-try (ICP-AES,IRIS Advantage, Thermo Jarrell Ash, USA); Cl− was

line spring/brine, groundwater, short-term stagnant surface water and long-term

titrated using the silver nitrate volumetric method with potassiumchromate as an indicator (DZG20.01-1991); SO4

2− was measuredby barium chloride titration with methyl orange as an indicator;HCO3

− and CO32− were measured by hydrochloric acid titration

with phenolphthalein and mixed solution of methylene blue andmethyl red as indicators (CO3

2− was undetected). Minor ions Sr2+,Li+, B3+, Br− and I− were measured by Inductively Coupled Plasmaand Mass Spectrometry (ICP-MS, Agilent 7500a, Agilent, USA). Cl−

and SO42− content in water samples with lower TDS (<1 g/L) were

also detected by Ion Chromatography (Dionex ICS900, USA). Br−,I− and B3+ (expressed as B2O3) were also detected using col-orimetry. TDS contents were estimated based on the conductivitymeasurements and the sum of total analyzed dissolved solids: afterfiltration, the filtrate was evaporated to dryness by water bath,then the solids left was processed with hydrogen dioxide solutionto remove organic substances; after being dried at 105–110 ◦C inthe oven for 2 h, the residue was cooled in desiccators to the con-stant weight (Editorial Board of Environmental Protection, 2002;The Ministry of Water Resources of the People’s Republic of China,1995; General Administration of Quality Supervision, Inspectionand Quarantine of the People’s Republic of China & StandardizationAdministration of the People’s Republic of China, 2008).

The oxygen and hydrogen isotope compositions were deter-mined using standard methods for waters (Epstein and Mayeda,1953; Coleman et al., 1982). The analytical precision for oxygen andhydrogen determinations is ±0.2‰ and 2‰ (MAT 253 stable isotoperatio mass spectrometer, Thermo Scientific, USA), respectively.

3.2. Data processing and analysis

Data on 537 samples were collected and analyzed, which weredivided into four groups-river water (n = 193), saline spring/brine(n = 196), groundwater (well water, n = 82) and stagnant surfacewater (short-term, n = 57; long-term, n = 9). Gibbs plot, Piper dia-gram (Piper, 1953), ration graphs of ions (in meq/L) were used to

study hydrochemical characteristics and controlling factors of dif-ferent waters in the Tarim Basin. Environmental background valuesof major and minor ions and TDS values in river water were calcu-lated with the SPSS 17.0 statistics software.

Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356 347

Table 2Statistical result of different waters of the Tarim Basin.

Water bodies Items K+ (mg/L) Na+ (g/L) Ca2+ (mg/L) Mg2+ (mg/L) Cl− (g/L) SO42− (g/L) HCO3

− (mg/L) TDS (g/L)

River water

na 163 140 193 193 193 193 186 166Maximum 213.512 7.663 515.370 411.273 5.632 4.922 537.289 17.894Median 4.649 0.084 58.605 22.195 0.089 0.198 113.778 0.596Mean 10.386 0.353 75.305 33.385 0.264 0.386 110.144 1.284Minimum 1.472 0.002 0.000 0.000 0.000 0.008 0.086 0.163

Saline spring/brine

n 184 192 196 196 196 196 185 191Maximum 2135.000 133.104 14,890.000 10,113.000 196.942 76.660 882.637 371.057Median 107.000 81.063 1808.000 556.000 129.869 3.429 48.260 227.678Mean 169.000 70.135 2940.000 1166.000 111.692 4.697 99.162 190.176Minimum 5.000 0.817 4.000 0.000 0.668 0.062 0.000 4.003

Groundwater

n 32 28 53 53 53 53 53 30Maximum 127.593 19.735 1567.830 838.400 31.049 4.895 813.000 57.862Median 6.271 0.137 90.298 67.630 0.380 0.523 73.224 0.908Mean 18.921 1.418 167.078 153.743 1.886 1.094 107.120 4.479Minimum 0.972 0.006 9.900 2.393 0.033 0.086 0.086 0.239

Short-termstagnant surfacewater

n 41 34 57 57 57 57 57 50Maximum 726.123 25.148 1073.846 4437.602 30.328 31.822 675.100 92.168Median 25.468 0.751 276.462 230.000 1.640 1.495 134.244 5.593Mean 70.114 3.006 341.935 532.377 4.042 3.083 159.011 11.784Minimum 0.166 0.008 0.054 0.003 0.033 0.041 0.089 0.309

Long-termstagnant surfacewater

n 9 7 9 9 9 9 9 9Maximum 2218.964 22.371 940.000 3828.831 13.667 45.499 970.900 88.560Median 18.203 0.650 50.743 373.821 0.325 0.601 153.236 1.682Mean 284.064 4.294 188.867 656.428 2.584 6.349 272.584 13.674Minimum 2.490 0.306 0.046 0.003 0.100 0.154 18.388 0.822

Water bodies Items Sr2+ (mg/L) Li+ (mg/L) I− (mg/L) Br− (mg/L) B2O3 (mg/L) pH

River water

n 158 158 158 158 147 72Maximum 12.177 1.257 0.149 7.738 30.821 5.55Median 0.568 0.05 0.034 0.235 0.445 7.72Mean 1.203 0.084 0.034 1.303 1.602 7.67Minimum 0.000 0.000 0.000 0.000 0.000 8.52

Saline spring

n 122 122 58 177 141 15Maximum 455.440 46.450 13.950 147.430 115.172 8.39Median 18.285 2.79 0.122 2.16 5.004 7.00Mean 73.248 11.272 1.447 11.842 12.408 6.97Minimum 0.457 0.000 0.000 0.000 0.000 5.22

Groundwater

n 30 31 31 32 23 12Maximum 23.035 0.795 0.102 7.738 18.648 8.01Median 1.213 0.036 0.031 0.461 0.46 7.51Mean 2.91 0.09 0.032 2.038 3.388 7.56Minimum 0.248 0.000 0.000 0.065 0.218 7.16

Short-termstagnant surfacewater

n 41 41 41 41 24 –Maximum 26.806 1.663 1.038 41.265 29.286 –Median 5.953 0.083 0.02 2.381 0.631 –Mean 5.633 0.213 0.076 3.468 3.099 –Minimum 0.001 0.000 0.000 0.001 0.139 –

Long-termstagnant surface

n 9 9 9 9 6 –Maximum 14.490 16.575 0.342 7.530 40.880 –Median 0.846 0.070 0.056 2.381 1.054 –

ions’

w(cbi(lur(e

esta

water Mean 4.167 2.010Minimum 0.001 0.020

a n – the sample size of each item; this is the same in statistical result of TDS and

In this study, boxplot was used for rejection of unusual values,hich has its own superiority in the recognition of unusual values

Zhuang, 2003; Wang, 2011), especially for large amounts of geo-hemical data processing. After the unusual values were rejectedy boxplot with SPSS 17.0 software step by step till each value was

n the normal scope and achieved the normal analytical conditionsChang et al., 2005), then the arithmetic mean value of the dataeft was calculated, i.e. the background value. The lower limit ofnusual values can be obtained by adding two times of the cor-esponding standard deviation (SD) to the arithmetic mean valueLi, 1983, 1991; Qiu and Huang, 1994; Huang and Xu, 2008; Zhangt al., 2011), which has greatly saved the computing time.

Gibbs plot (Gibbs, 1970) is a useful tool for surface water

volution mechanism study, and through plots of total dissolvedolids (TDS) versus the sodium to sodium plus calcium ratio andhe chloride to chloride plus bicarbonate ratio, i.e. Na/(Na + Ca)nd Cl/(Cl + HCO3), material sources of natural waters can be

0.077 3.089 7.828 –0.000 0.225 0.528 –

contents of other water bodies.

effectively distinguished: atmospheric precipitation, rock domi-nance and the evaporation-fractional crystallization process. Thisstudy has shown proof positive why many scholars have used thismodel to study relationships between chemical composition ofwaters and regional climate, geological features, etc. (Larsen et al.,2011; Edet and Okereke, 2005; Min et al., 2007; Zhu and Yang, 2007;Al-Shaibani, 2008; Hou et al., 2009; Bonotto and De Lima, 2010;Song et al., 2010; Ye et al., 2010). So, in this research, Gibbs plotalso takes a great role in data analysis.

4. Results

4.1. General characteristics and isotopic compositions of waters

Chemical and isotopic analyses of waters were undertaken as abasis for investigating the hydrochemical characteristics and con-trolling factors in the Tarim Basin. Statistical results of major and

348 Y. Bo et al. / Chemie der Erd

Fig. 3. Plot of �18O-�D for waters from the Tarim Basin only water samples fromRwW

mTottsigs0fa0w

lLblmid

a�(eo(fceafbstma3c

egion 3 and Region 4, as well as two subsurface brine samples from the Lop Nurere collected and analyzed; most data for subsurface brine of Lop Nur are fromang et al. (2001).

inor ions’ content and TDS value of different waters are shown inable 2. Saline spring/brine shows much higher level of TDS, thanther water bodies with a median TDS value of 227.678 g/L, andhe maximum is 371.057 g/L. Besides, some phreatic groundwa-er and stagnant surface water (ditch water and salt lake water)amples, as well as river water flowing through salt-rock bear-ng areas, also have relatively higher TDS values. TDS range ofroundwater, short-term stagnant surface water and long-termtagnant surface water is 0.239–57.862 g/L, 0.309–92.168 g/L, and.822–88.560 g/L, respectively. While for river water, TDS rangesrom 0.163 g/L to 17.894 g/L, and the median is 0.596 g/L; these arell higher than those of the Qaidam Basin river water (ranges from.126 to 0.778 g/L) (Zhou and Dong, 2002). Among all the159 riverater samples, 11 show TDS values higher than 3 g/L.

Saline spring/brine and other water samples with higher TDSevel contain higher content of K+, Na+, Ca2+, Mg2+, Cl−, SO4

2−, Sr2+,i+, Br−, I−, and B (B2O3), while HCO3

− content in different waterodies show small differences. Besides, saline spring/brine show

ower pH value (Table 2) than river water and groundwater, with aedian pH value of 7.00, and that of river water and groundwater

s 7.72 and 7.51, respectively. pH value for the same water body inifferent regions show small differences.

On a global average, the general relation between �18Ond �D for natural waters can be expressed by the equation:D = 8�18O + 10 (Craig, 1961), i.e. the Global Meteoric Water LineGMWL). As shown in Fig. 3, isotopic compositions of differ-nt water types show great differences. Isotopic compositionsf river water, groundwater and some stagnant surface waterfrom both region 3 and region 4), as well one meteoric waterrom Lop Nur, fall very close to the GMWL on the left, whichlearly prove that they originate from regional precipitation. How-ver, isotopic compositions of subsurface brine from Lop Nurnd a part of saline spring/brine from region 4 fall far awayrom the GMWL on the right, revealing strong evaporation therine suffered during their evolution. Data points of other salinepring/brine and other stagnant surface water fall just betweenhe two groups mentioned above, indicating both the source of

eteoric water and the effect of evaporation. Besides, oxygennd hydrogen isotopic compositions for groundwater (from region) and saline spring/brine (from region 4) show good positiveorrelations. The regression line for groundwater data plotted in

e 73 (2013) 343– 356

Fig. 3 is: �D = 9.2593�18O + 26.033 (r = 0.9921) and that for salinespring/bring is: �D = 2.8764�18O + 49.668 (r = 0.8455).

4.2. Environmental background values of river water

Element background value reflects the basic geochemical con-ditions of element distribution in a region. Background values ofmajor and minor ions and TDS in river water of four regions areshown in Table 3 (sample size of Region 5 is too small to beinvolved). TDS background values are:

• Region 1 (the south and southeast, 0.923 g/L) and• Region 2 (the southwest, 0.824 g/L) are higher than• Region 3 (the northwest, 0.446 g/L) and• Region 4 (the north, 0.444 g/L). This is related to the climate of

the basin-the north is wetter and the south is drier (Lv, 1993).

Background value range of K+, Na+, Cl−, Ca2+ is3.823–8.895 mg/L, 0.042–0.244 g/L, 0.039–0.164 g/L and51.174–65.247 mg/L respectively; there are small differencesamong background values of Mg2+ in these four regions, the rangeis 22.077–26.003 mg/L; background value range of HCO3

− andSO4

2− is 35.573–165.023 mg/L and 0.206–0.282 g/L, respectively.In addition, based on background value (bij) of each analytical

item (i) in the four regions and its corresponding valid sample size(nij), background value of each item in river water in the Tarim Basin(Bi) has been calculated (Table 4), according to Eqs. (A.1) and (A.2).

Bi =4∑

i=1

bij × kij (A.1)

ki = nij

4∑

j=1

nij

(A.2)

Background values listed in Table 4 above can help to under-stand the overall characteristics of river water in the Tarim Basin.However, in future practical work, background values of eachregion may be referred more often in regional studies, and lowerlimit of unusual values for each item (mij) can be calculated basedon its standard deviation (SD) value (ıij) and background value (bij),i.e. mij = bij + 2ıij.

In comparison with river water of the Qaidam Basin (Zhou andDong, 2002), background values of major ions (K+, Na+, Mg2+, Cl−

and SO42−) for river water of the Tarim Basin are higher than those

of the Qaidam Basin (3.666 mg/L, 0.084 g/L, 19.119 mg/L, 0.051 g/L,0.045 g/L, respectively), while the Qaidam Basin river water con-tains higher level of Ca2+ (65.316 mg/L) and HCO3

− (141.115 mg/L)because of its local marble, dolomite, limestone, etc. Besides, back-ground value ratio of SO4

2− to Cl− (SO4/Cl) of river water in theTarim Basin (2.75) is much higher than that of river water in theQaidam Basin (0.88) and seawater (0.14)-8 times higher than sea-water and two times higher than river water of the Qaidam Basin;the K+ to Cl− ratio (K/Cl) of river water in the Tarim Basin is twotimes higher than seawater, and slightly lower than that in theQaidam Basin (Table 5).

4.3. Hydrochemical types of waters

According to Valyashko’s classification (Valyashko, 1965), water

samples in the Tarim Basin are divided into the chloride type, mag-nesium sulfate subtype, sodium sulfate subtype and carbonate type.Hydrochemical type of waters in the Tarim Basin shows zonal dis-tribution (Fig. 4).

Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356 349

Table 3Statistical result of environmental background values in river water of different regions in the Tarim Basin.

Nb Minimum Maximum Mean SD N Minimum Maximum Mean SD

Region 1 (n = 37) Region 2 (n = 25)K+ (mg/L) 18 4.563 15.614 8.895 3.067 K+ (mg/L) 16 2.021 13.199 6.127 2.827Na+ (g/L) 19 0.042 0.659 0.244 0.182 Na+ (g/L) 13 0.036 0.340 0.141 0.088Ca2+ (mg/L) 36 0.026 212.978 57.854 61.570 Ca2+ (mg/L) 25 0.048 155.088 51.174 50.073Mg2+ (mg/L) 36 0.001 67.540 24.279 20.077 Mg2+ (mg/L) 25 0.001 72.968 22.077 24.003Sr2+ (mg/L) 8 0.001 0.002 0.001 0.000 Sr2+ (mg/L) 15 0.000 1.099 0.294 0.393Li+ (mg/L) 12 0.032 0.064 0.042 0.009 Li+ (mg/L) 17 0.008 0.141 0.052 0.041Cl− (g/L) 31 0.055 0.325 0.164 0.073 Cl− (g/L) 21 0.037 0.254 0.113 0.065SO4

2− (g/L) 33 0.064 0.757 0.272 0.206 SO42− (g/L) 22 0.090 0.513 0.225 0.127

I− (mg/L) 19 0.044 0.067 0.059 0.006 I− (mg/L) 17 0.047 0.073 0.058 0.009Br− (mg/L) 17 2.024 3.393 2.475 0.384 Br− (mg/L) 7 2.381 2.381 2.381 0.000B2O3 (mg/L) 18 0.646 9.234 3.043 2.933 B2O3 (mg/L) 13 0.220 1.081 0.541 0.261HCO3

− (mg/L) 33 22.066 309.109 165.023 61.071 HCO3− (mg/L) 23 98.071 232.800 144.374 36.558

TDS (g/L) 33 0.351 1.864 0.923 0.422 TDS (g/L) 22 0.412 1.675 0.824 0.404Region 3 (n = 35) Region 4 (n = 94)K+ (mg/L) 28 1.494 9.713 4.464 1.494 K+ (mg/L) 77 1.472 7.951 3.823 1.625Na+ (g/L) 28 0.016 0.170 0.066 0.016 Na+ (g/L) 44 0.000 0.101 0.042 0.027Ca2+ (mg/L) 31 0.044 146.014 63.867 0.044 Ca2+ (mg/L) 87 0.000 125.071 65.247 26.074Mg2+ (mg/L) 28 0.002 69.953 26.003 0.002 Mg2+ (mg/L) 88 0.000 64.947 24.637 15.182Sr2+ (mg/L) 32 0.001 4.143 1.323 0.001 Sr2+ (mg/L) 65 0.010 1.216 0.511 0.223Li+ (mg/L) 23 0.035 0.070 0.054 0.035 Li+ (mg/L) 79 0.000 0.087 0.039 0.023Cl− (g/L) 28 0.014 0.152 0.061 0.014 Cl− (g/L) 56 0.009 0.067 0.039 0.016SO4

2− (g/L) 34 0.008 0.975 0.282 0.008 SO42− (g/L) 86 0.045 0.489 0.206 0.107

I− (mg/L) 33 0.002 0.082 0.024 0.002 I− (mg/L) 86 0.000 0.092 0.025 0.023Br− (mg/L) 32 0.000 4.819 1.062 0.000 Br− (mg/L) 66 0.000 0.369 0.103 0.097B2O3 (mg/L) 27 0.000 1.470 0.448 0.000 B2O3 (mg/L) 68 0.056 0.733 0.320 0.163HCO − (mg/L) 34 49.035 269.500 155.101 49.035 HCO − (mg/L) 85 0.086 173.900 35.373 55.609

T

•

•

•

3

TDS (g/L) 23 0.240 0.667 0.446 0.240

b N – the valid sample size involved in background value calculation.

In Region 1 and Region 2, the carbonate type and the sodium sul-fate subtype dominate, and seldom exists the magnesium sulfatesubtype;In Region 3, waters mainly belong to the sodium sulfate sub-type, and partially belong to the magnesium sulfate subtype and

chloride type;In Region 4, the sulfate types (the magnesium sulfate subtype andthe sodium sulfate subtype) dominate, with a small part belong-ing to the chloride type.

Fig. 4. Distribution of hydrochemi

3

DS (g/L) 48 0.163 0.900 0.444 0.160

Besides, hydrochemical types of different waters also showzonal distribution.

• River waters in Region 1 and Region 2 mainly belong to the car-bonate type and the sodium sulfate subtype;

• River waters in Region 3 mainly belong to the sodium sulfatesubtype;

• River waters in Region 4 mainly belong to the sulfate types, witha small part belonging to the chloride type;

cal types in the Tarim Basin.

350 Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356

F Basin1 eans

•

•

TSB

ig. 5. Piper plots of chemical compositions for different types of water in the Tarim to group 5 in Fig. 4 represents Region 1 to Region 5, respectively; the apex of Na m

The only one river water sample from Region 5 belongs to the

magnesium subtype.Groundwaters in Region 1, Region 2, Region 3 and Region 5 mainlybelong to the sodium sulfate subtype, with a few belonging to themagnesium subtype or the carbonate type;

able 4tatistical result of environmental background values in river water of the Tarimasin.

Items Background value Items Background value

K+ (mg/L) 4.924 SO42− (g/L) 0.242

Na+ (g/L) 0.102 I− (mg/L) 0.033Ca2+ (mg/L) 60.778 Br− (mg/L) 0.834Mg2+ (mg/L) 24.640 B2O3 (mg/L) 0.767Sr2+ (mg/L) 0.669 HCO3

− (mg/L) 89.249Li+ (mg/L) 0.044 TDS (g/L) 0.685Cl− (g/L) 0.088

. (a) River water; (b) saline spring/brine; (c) ground water; (d) surface water. Group the sum of Na+ and K+.

• Groundwaters in Region 4 mainly belong to the sulfate types, and

few belong to the chloride type.

• Saline springs/brines in Region 1, Region 2 and Region 3 mainlybelong to the sulfate types, and few belong to the chloride type;

Table 5Comparision of main ions’ contents and ratios for river water of the Tarim Basin andthe Qaidam Basin with seawater.

Water K+ (mg/L) Cl− (mg/L) SO42− (mg/L) K/Cl SO4/Cl

River water in theTarim Basin

4.92 88 242 0.06 2.75

Sea watera 429 20,057 2784 0.02 0.14River water in the

Qaidam Basinb3.67 51 45 0.07 0.88

a From Drever (1988).b From Zhou and Dong (2002).

Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356 351

F s for Rp f Na+

v

•

CiL1cwsf

gs

ig. 6. Relation graphs of ions (in meq/L) in river water of the Tarim Basin. 1–5 standlot of HCO3

− versus (Ca2+ + Mg2+); (c) the plot of (Na+ + K+) versus Cl−; (d) the plot oersus Cl− .

Saline springs/brines in Region 4 mainly belong to the chloride,followed by the sulfate types.

Chloride type water usually reveals recharge of hydrothermala–Cl brine, which means fluids from the deep join the hydrochem-

cal evolution of the Tarim Basin (Lei and Xu, 1999; Yang et al., 1993;owenstein and Risacher, 2009). Stagnant surface waters in Region

and Region 2 belong to the magnesium sulfate subtype and thearbonate type; in Region 3 the sodium sulfate subtype dominates,ith few belonging to the magnesium sulfate subtype; stagnant

urface waters in Region 4 mainly belong to the sulfate types, and

ew belong to the chloride type.

Additionally, in Lop Nur playa, there exists plenty of under-round potassium-rich brine, which belongs to magnesium sulfateubtype (Wang et al., 2001).

egion 1 to Region 5, respectively; (a) the plot of (Cl− + SO42−) versus HCO3

−; (b) theversus SO4

2−; (e) the plot of (Ca2+ + Mg2+) versus SO42−; (f) the plot of (Ca2+ + Mg2+)

4.4. Water chemical composition and controlling factors

4.4.1. River waterChemical compositions for river water in different regions of the

Tarim Basin can be seen in Fig. 5a. HCO3− contents are mostly less

than 40% of the total anions, except several data points of Region3 (40–80%). Cl− and SO4

2− are the main anions in Region 4, withquite a few projection points of anions falling on the SO4

2−–Cl−

line. As for cations, Mg2+ contents in most river water samples arebelow 40% and Ca2+ are mostly 20–80%. Besides, more than ten datapoints of Region 1 and Region 2 fall on the (Na+ + K+) apex, and this

is greatly relevant to the weathering of rocks (granite, gneiss andother metamorphic rocks, etc.) of the surrounding mountains.

Furthermore, ration graphs of ions can also help to understandmaterial source of river water in different regions of the basin.

352 Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356

mine m

FsmaroiF3ls5fs

CFrdeidlw

wocgRsw

Fig. 7. Gibbs plots indicating the mechanisms that deter

ig. 6a reveals that the evaporite is a more important materialource of most river waters than the carbonatite in the basin, forost data points are projected below the equivalence line except

small part of Region 3. Fig. 6c implies that Na+, K+ and Cl− iniver water of the Tarim Basin primarily come from the solutionf halite and sylvine, and Fig. 6d shows that the sulfate is also anmportant source of Na+. From Fig. 6e, combined with Fig. 6b andig. 6f, the sulfate is the main source of Ca2+ and Mg2+ in Region

and Region 4, while Ca2+and Mg2+ in Region 1 and Region 2 areess relevant to the evaporite or the carbonatite, so they may haveomething to do with the silicate. For the only one sample of Region, Ca2+, Mg2+ and SO4

2− mostly come from the solution of the sul-ate, and Na+, K+ and Cl− come from the solution of halite andylvine.

Gibbs plots of TDS versus the ion ratios Na/(Na + Ca) andl/(Cl + HCO3) of river water in the Tarim Basin are shown inig. 7. Most data points fall on the intermediate area between theock dominance end member and the evaporation/precipitationominance end member. This indicates that rock weathering andvaporation are the dominant processes controlling the major-on composition of river water in the Tarim Basin. Besides, someata points approaching to the Na/(Na + Ca) = 1 or Cl/(Cl + HCO3) = 1

ine reveal the evaporation of atmospheric precipitation dominatedater.

Totally, besides evaporation, chemical composition of riverater in the Tarim Basin is greatly influenced by rocks and minerals

f the surrounding mountains. In Region 1 and Region 2, chemi-al composition of river water is mainly influenced by the granite,

neiss and other metamorphic rocks, etc., while in Region 3 andegion 4, it is mainly influenced by the dissolution of evaporite,uch as gypsum and halite rocks, and chemical composition of riverater in Region 3 is partially influenced by the carbonatite.

ajor-ion composition of river water in the Tarim Basin.

4.4.2. Saline spring/brineChemical compositions for saline spring/brine in different

regions are shown in Fig. 5b. For anions, most data points fall onthe SO4

2−–Cl− line, and approach the Cl− apex in the anions’ tri-angular plot, with Cl− accounting for more than 60%. Besides, mostdata points approach the (Na+ + K+) apex in the cations’ triangu-lar plot, and contents of Mg2+ and Ca 2+, are lower than 30% ofthe total anions. All the saline spring samples are characterized bythe major anion pattern Cl− > SO4

2− > HCO3−. From the Gibbs plot

(Fig. 8a), chemical compositions of saline spring in the Tarim basinare mainly controlled by evaporation, for all data points fall on theevaporation/precipitation end member, similar with the composi-tion of seawater.

4.4.3. GroundwaterFrom the Piper plot (Fig. 5c), groundwater in Region 1 and

Region 2 have similar compositions, the data points of cationsare close to the (Na+ + K+) apex, and SO4

2− and Cl− dominate inthe anions. Data points of anions of Region 3 approach to theSO4

2− apex, and the compositions of cations are similar withthose of Region 1, Region 2 and Region 5. In Region 4, Ca2+andMg2+are the main cations, while SO4

2− is the main anion, withmost data points falling on the SO4

2−–Cl− line. Groundwater inRegion 5 (n = 13) has stable chemical composition. The Gibbs plot(Fig. 8b) reveals that chemical compositions of groundwater in dif-ferent regions are different. Groundwater composition of Region3 is controlled by evaporation and rock weathering, and that of

Region 4 is controlled by evaporation of atmospheric precipitationdominated water, while chemical composition of groundwater inRegion 5-the central desert area, is mainly controlled by evapora-tion.

Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356 353

F sition of saline spring (a), groundwater (b) and stagnant surface water (c) in the TarimB

4

fcwiwccei

5

5

ladbNaeTdasm1

sta

ig. 8. Gibbs plots indicating the mechanisms that determine major-anion compoasin.

.4.4. Stagnant surface waterAs shown in Fig. 5d, most data points of anions in stagnant sur-

ace water fall on or approach the SO42−–Cl− line. The chemical

omposition of stagnant surface water in Region 5 is quite stable,ith Cl− accounting for more than 60% and (Na+ + K+) account-

ng for more than 40%. Chemical compositions of stagnant surfaceater in the other four regions are less stable, especially cations’

omposition of Region 4. From the Gibbs plot (Fig. 8c), chemicalomposition of stagnant surface water is primarily controlled byvaporation, and partially (in Region 4) influenced by rock weather-ng and evaporation of atmospheric precipitation dominated water.

. Discussion

.1. Recharge of hydrothermal Ca–Cl brines

Lowenstein and Risacher (2009) studied closed basin brine evo-ution and the influence of Ca–Cl inflow waters (Death Valleynd Bristol Dry Lake California, Qaidam Basin, China, and Salare Atacama, Chile). They called those brines hydrothermal Ca–Clrines. Diagenetic-hydrothermal waters are typically brines (rich ina–Ca–Cl) that contain little SO4 or HCO3, which reflects the inter-ctions between heated groundwaters and sediments or rocks atlevated temperatures, commonly 100 ◦C to >300 ◦C (Hardie, 1990).hey have Ca equivalents > SO4 + HCO3 + CO3 and are commonlyischarged as springs or seeps at low temperatures (Lowensteinnd Risacher, 2009). Hydrothermal Ca–Cl brines can reach theurface by convection-driven circulation associated with ther-al anomalies or by topographically driven circulation (Hardie,

990).

In this study, chloride type of waters are widely distributed in

aline springs/brines of Region 4-the Kuqa Basin, where two bigectonic fault belts (Qiulitage in the south and Kelasu in the north)re distributed from the east to the west. These waters have Ca

Fig. 9. Ternary Ca–SO4–Cl phase diagrama for saline springs/brines in the TarimBasin.

Modified from Lowenstein and Risacher (2009).

equivalents > SO4 + HCO3 + CO3 and here they are also calledhydrothermal Ca–Cl brines. From Fig. 9, they are chemically dis-tinct from meteoric weathering water because they fall within theCa–Cl field. Besides, some data points of river water, groundwaterand stagnant surface water also fall in the Ca–Cl field (the chloridetype of water referred in Section 4.3) in Region 4. HydrothermalCa–Cl brines reflect interactions between groundwaters and rocksor sediments at elevated temperature (Lowenstein and Risacher,2009). Therefore, in the Tarim Basin, hydrothermal Ca–Cl brines

from the deep within the earth not only are the main recharge forsaline springs/brines but also join the evolution of other waters(river water, groundwater and stagnant surface water).

354 Y. Bo et al. / Chemie der Erde 73 (2013) 343– 356

nd ev

5

p1gom

Brtoomrmei

5

BtnewsBsesh

ctfeNfoo

6

c

Fig. 10. Water circulation a

.2. Material sources of Lop Nur

In Lop Nur, a huge liquid potash ore deposit (a great deal ofotassium-rich brine reserved in pores of glauberite) was found in995. However, till now the formation mechanism of the brine andlauberite is not quite clear (Liu et al., 2007; Ma, 2010). The sourcesf Ca2+, K+ and SO4

2−, as well as the reason that the brine containsuch higher level of SO4

2− than Cl−, are still unknown.In this study, some very important clues have been found.

ecause of strong evaporation and weathering of the surroundingocks, river waters in the Tarim Basin mostly belong to the sulfateypes, which are greatly different from river waters in other areasf the world (the carbonate type dominates). Besides, higher levelf background value ratios SO4/Cl (2.75) and K/Cl (0.06) make itore reasonable that the inflow waters of Lop Nur are relatively

icher in K+ and SO42−, while relatively poorer in Cl−. Further-

ore, recharge of hydrothermal Ca-Cl brines from deep within thearth bring abundant Ca2+ to the Tarim Basin and finally become anmportant material source for glauberite accumulation in Lop Nur.

.3. Water evolution in the Tarim Basin

Water evolution is a very complicated process in the Tarimasin. River water plays an important role in water evolution ofhe Tarim Basin, however, the participation of other waters is notegligible, especially saline springs/brines. As for the influence ofvaporation, oxygen and hydrogen isotopic compositions in riverater, groundwater, stagnant surface water, saline spring and sub-

urface brine in Lop Nur show water evolution process of the Tarimasin stage by stage: river water, groundwater and part of stagnanturface water show recharge from meteoric water with weakervaporation, other stagnant surface water and saline spring revealtrong evaporation, and subsurface brine in Lop Nur represents theighest stage of water evolution in the Tarim Basin.

Based on closure and one-way incline of the Tarim Basin, waterirculation and evolution are suggested as shown in Fig. 10: sincehe uplift of the western Tarim Basin, a great deal of waters (sur-ace waters and groundwater, as well as brine from deep within thearth) had been forced to lower places and finally gathered in Lopur Lake; because of high temperature and aridness, waters suf-

ered from strong evaporation and the salts began to precipitate;ver a long period of time, the lake dried up with plenty of salts andther minerals accumulated.

. Conclusions

Determination of element background value for river wateran offer essential data information for research on basic

olution of the Tarim Basin.

hydrogeochemical characteristics of the Tarim Basin. In compari-son with river water of the Qaidam Basin and seawater, backgroundvalue ratio SO4/Cl for river water of the Tarim Basin is 18 timeshigher than seawater and two times higher that river water of theQaidam Basin; the ratio K/Cl for river water of the Tarim Basin andthe Qaidam Basin are two times higher than seawater. This revealsthat the material source of Lop Nur is relatively richer in SO4

2−

and K+ and poorer in Cl−, which may give a reasonable explanationfor the accumulation of abundant glauberite and potassium in LopNur.

Hydrochemical types and chemical compositions of differentwater bodies in the Tarim Basin show zonal distribution. Riverwater compositions of the Tarim Basin are greatly related to thesurrounding rock types and strong evaporation. As for effect of rockweathering, chemical compositions of river water in the north andthe northwest of the basin are greatly influenced by the dissolutionof evaporite (halite and gypsum, etc.), so the sulfate types waterdominate. While water compositions in the south and southeast aregreatly influenced by the granite, the gneiss and other metamorphicrocks, etc., so the carbonate type and the sodium sulfate subtypewater dominate. Groundwater, saline spring, as well as stagnantsurface water in the Tarim basin also suffer strong evaporation,and compositions of these waters are also more or less controlledby rock weathering. Moreover, the wide distribution of chloridetype water proves that hydrothermal Ca-Cl brines from the deepplay an important role in the hydrochemical evolution of the TarimBasin.

Acknowledgements

National Key Basic Research and Development Program (973program, No. 2011CB403007) and National Natural Science Foun-dation of China (No. 40830420) from the Chinese governmentprovided the funding for this study. We are grateful to graduatestudents Chao Gao and Xianfu Zhao of Chinese Geology Univer-sity (Beijing) for their help in sample collecting. We also wouldlike to kindly acknowledge the NRCGA (National Research Cen-ter for Geoanalysis), Yingsu Wang, Meifang Dai et al., for theirhard work in water sample analysis. Besides, Ph.D. student HuaZhang of Chinese Academy of Geological Sciences is thanked forhis help in part of graph drawing and Ph.D. student WenxiangWang of Chinese Geology University (Beijing) is thanked for his

help in data collection from literatures. Mr. Tim Swanson is thankedfor his revision of English. Prof. Liqiang Luo and two anonymousreviewers are thanked for their constructive comments on themanuscript.

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