Characterizing Interactions Between Surface Water and Groundwater Injialu the River Basin Using Majorchemistry Ion and Stable Isotopes L

Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Sciences Discussions Earth System 3 Hydrology and , and D. Long 1,2 , B. Zhang 1 5956 5955 , D. Han 1 in North Zhengzhou City increased prominently due to the − -N) in water within the Zhengzhou region (Lu et al., 2008) and 3 , Y. Zhang 1 , X. Song 1,2 This discussion paper is/has been under review for the journal Hydrology and Earth System Sciences (HESS). Please refer to the corresponding final paper in HESS if available. Key Laboratory of Water Cycle and Related Land Surface Processes, Institute of Geographic Graduate University of Chinese AcademyBureau of of Sciences, Economic 100049 Geology, Beijing, Jackson China School of Geosciences, The University of Texas at ammonia nitrogen (NH the lower reaches in the Zhoukou region (Zhao et al., 2005; Xie et al., 2008). Zhang river-aquifer interface and ultimately benefit water management in the future. 1 Introduction The Jialu River (JR), theinated secondary by tributary a of varietyand the of the Huaihe untreated contaminant River, or is sources lightly severelyThese treated such contam- wastes sewage have as wastes resulted a in in some elevated large concentrations cities of number (Zhang chemical et of oxygen al., (COD) trade 2009). and wastes tional well (location SY3) seemedSeptember to 2010. be Fractional recharged contributions byculated river of based water river on via water isotopic bank and to infiltrationshow chemical in that the data the groundwater groundwater using was were a approximately mass-balance cal- composedfindings of approach. would 60–70 be Results % useful river for water. These a better understanding of hydrogeological processes at the study aims to characterizelakes the and relationships rivers) and betweenThe surface groundwater concentration water near of (e.g. Cl thedischarge reservoirs, of river a in large the amountconcentrations of shallow in domestic Quaternary water. groundwater Nitrate in aquifer. andto Fugou potassium the show County. use maximum These of highwith a a large levels quantity constant can of stable beor fertilizer isotopic attributed over signature, rarely this which receive region. illustrates The recharge that regional the from well groundwater surface had never water water. However, the groundwater of transi- The Jialu River, a secondaryinated tributary for of the the Huaihe majortreated River, has sewage contaminant been wastes sources, severely in contam- suchcomponent some of as cities. the hydrologic Groundwater a system, along but number instead the connected of river with the untreated is surface water. not or This an lightly isolated Abstract Hydrol. Earth Syst. Sci. Discuss.,www.hydrol-earth-syst-sci-discuss.net/9/5955/2012/ 9, 5955–5981, 2012 doi:10.5194/hessd-9-5955-2012 © Author(s) 2012. CC Attribution 3.0 License. Characterizing interactions between surface water and groundwater inJialu the River basin using majorchemistry ion and stable isotopes L. Yang 1 Sciences and Natural Resources Research,100101 Chinese Beijing, Academy China of2 Sciences, 3 Austin, Austin, 78758 TX, USA Received: 31 March 2012 – Accepted: 20Correspondence April to: 2012 L. – Yang ([email protected]), Published: X. 9 Song May ([email protected]) Published 2012 by Copernicus Publications on behalf of the European Geosciences Union. 5 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | C ◦ and 00 ). 17.9 47 − 0 37 ◦ E (Fig. 1). As a sec- C, and the maximum 00 ◦ 7 0 38 ◦ http://cdc.cma.gov.cn/ and 114 00 C and minimum in February of 17 ◦ 0 6 ◦ , ranging in latitude between 33 5958 5957 2 ). ective management of water resources over this region. However, the ff N and in longitude betwen 113 00 50 http://www.ngac.cn 0 53 ◦ The geology of this study area is relatively complex (Fig. 3). This study area pertains The climate throughout the study area is with warm, moist summers and cool, dry Two field campaigns for investigating the interaction between surface water and The Jialu River basin (JRB) aquifer is the primary source of drinking water for the campaign was inZhengzhou flooding on 18 processing. July 2010 Water before the samples rainy event. were It began taken to lightly in rain in Xingyang the and evening and Pleistocene lacustrine-alluvium, alluvium-diluvium,(clay, and silt slope-diluvium sand, sediments fine sand,China, sand and gravel; data from National Geological Archives of 3 Sampling and analytical methods Two major sampling campaignsaquifer were up carried to out 1.5 km along from the the JR river and in surrounding July and JRB September 2010, respectively. The first to one of the transitionaleast. areas between The the upper mountains reaches in ofschist the west the and and JRB Cambrian the are plains sedimentary dominatedstone). in The by the rocks lower Paleoproterozoic (i.e. reaches quartzite are sandstone, and composed limestone, mainly of shale, Holocene and alluvium, aeolian mud- deposit winters. The average annual temperatureis in observed Zhengzhou in is July 14.4 between with extreme 1951 value and of 2010. 43 per The year mean from annual 1951to precipitation to maximum in 2010, 1041 mm. Zhengzhou with Mostmonth was large of 641 period interannual mm the from variability precipitation from Junewhen falls through minimum precipitation in 381 September, the mm accounts i.e. form forfrom the of more China flood rain Meteorological than season Data during 65 Sharing of % the Service the 4- of System, river annual basin, precipitation (Fig. 2; data eastwardly and then southeastwardly throughin Weishi, the Fugou, Yinghe Xihua, and Rivereral lastly at tributaries. joining Zhoukou. The main The tributaries mainRiver. include Jialu the Suoxu River River, channel Donfengqu and is Shuangji contributed by sev- in Xinmi and Zhengzhou. From Zhengzhou, the river has two abrupt turns, i.e. flowing ondary tributary ofshuiyu the of Huaihe Xinmi River, in the Henan JR Province. is In its 220 km source long, region, originating the river from flows Shen- northeasterly was in flood processing, andof the this latter study one was was to afteralong characterize flood the relationships period. between JR. The surface overall water objective and groundwater 2 Study area The JRB covers an34 area of of 2750 km concern. An betteris understanding a of key the forpublished interactions e studies between did not the seem two to have water adequately bodies addressed thesegroundwater was issues. conducted in July and September 2010, respectively. The former one rapidly growing population ofnities. Zhongmou, Groundwater Weishi, and Fugou, surfacesystem, water Xihua but are and instead not nearby interact isolated with commu- matic components each landscapes of other (Winter the across et hydrologic a2002). al., variety Thus, of 1998; there physiographic Woessner, is andsediment 2000; a of cli- Winter, JR noteworthy 2001; could concern contaminate Sophocleous, chemistry that the JRB in the aquifer. response Temporal trace variations to in elements changes groundwater in in the river chemistry water and and stream flow are also of great enriched in theenrichment lower taking reaches place compared inet with al. the the (2011) lower showed upper elevated reachesnol stream, concentrations A of of with in nonylphenol, the the octylphenol, the Zhengzhou and JRto maximum bisphe- bed urban result sediment. in zone. Some potential Zhang of aquatic and the human-health elevated concentrations problems. were high enough et al. (2009) reported that concentrations of alkylphenols in surface water were more 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | axis , rep- ff + D) and δ )/TZ 10% in the − ± 1% ( TZ ± − + . Major cations were determined ) are generally in the charge bal- − − 3 was made and the negative charge − 3 4 measurements. However, the chemical + 4 , HCO , and Cl − − 3 5960 5959 , Cl − 3 , NO − 2 4 , NO − 2 4 O) were determined at IGSNRR, CAS using o , SO + 18 δ , SO ,K + + ,K + , Na D and + δ 2 , Na + 2 , Mg + O). 2 18 , Mg δ + 2 was measured by the diluted vitriol-methylic titration method using 0.0112 M . 4 − 3 SO Water isotopes ( The Normalized Inorganic Charge Balance, NICB, defined as (TZ Temperature, pH value and electrical conductivity of each sample were measured The water quality was measured at the Center for Physical and Chemical Analysis of Surface water samples were collected at nine locations (Fig. 1). The groundwater Surface water samples were typically collected at bridges in the reaches at a depth of 2 0.15% ( fected by water-rock reactions under normal1996). Therefore, temperatures isotopic (McCarthy variations et may al., occur within 1992; the Gat, catchment as a consequence thousand deviations from± the VSMOW with analytical precisions of 4 Results 4.1 Stable isotopic composition in waters Stable isotopic compositions in water can be considered conservative and hardly af- integrated-cavity output laser spectroscopy (Model DLT-100;and Los Gatos the Research method Inc.) describednal in laboratory Lis water et standardsStandard al. that Mean (2008). were Ocean All previously Water samples (VSMOW) calibrated were (0 relative ‰). normalized to Results to the were inter- expressed Vienna as parts per 1995; Huh et al., 1998).ions It (Ca was indicated byance. Huh A et few al. of (1998) these water thatexcess, samples or the showed some measured a inversely major charge with imbalancecould a with be negative a related charge positive to surplus. charge the This factsurplus that positive could no charge be analysis excess attributable of to PO analysis the results lack of were NH adopted whenstudy. the charge-balance error was within major anions were determined usingHCO ion chromatography (LC-10A, Shimadzu, Japan). H resents the deviation extent between the total cations and total anions (Edmond et al., using Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES), while including Ca locate the sampling locations. in situ using aand WM-22EP handled redox electrical potential conductivityParameter were meter. Digital Oxygen also Meter. concentration The determined field watervalues using quality were parameters stabilized. a were Hach monitored until HQ30d these Single-Input Multi- Institute of Geographic Sciences andof Natural Resources Sciences Research, (IGSNRR, Chinese Academy CAS). All samples were analyzed for major ion composition, about 30 cm using awells weighted polyethylene were water selected collector. The forto existing sampling store village-supply groundwater. the The unfiltered 100before stream ml samples the polyethylene were final bottles pre-rinsed water used tape with sample so sample was as water three to acquired. times prevent All evaporation. samples The were global sealed positioning system with (GPS) adhesive was used to 2010, i.e. the second campaign was carried out duringsamples the post-flood were period. taken fromdepths of 9 the domestic wells wellsQilijing ranged and in between Xihua, 9 and the m 50 m quaternary (locationthe (location SY14 investigated J5 aquifer area and in where (Table Fig. the SY16 3). 1) surface in elevation into The is Xingyang, Fig. the approximately the 156 sea 1) northwestern m level. in with part reference Fugou of 102 mm until 08:00 a.m. LTa (local time). high The stage. JR Riverflood rose water peak quickly passed. (location from However, a J10, theflood low SY12, river peak flow water did and stages SY9 not to SY15) reach and10 had the SY20 September locations. been had 2010. The been sampled second A sampled campaign when 121.6 when mm was conduced rainfall from was 8 observed to between 5 and 7 September of 18 July and became more intense after the midnight. The rainfall amount was up to 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | + 2 with 1 − C. Most ◦ and Ca − 2 4 D values changed δ , respectively. Most part 1 − 0.86), which also reflects the = 2 R 3.34‰, and the − in September 2010. The former EC re- 1 − and 0.36–7.09 mgl 5962 5961 1 − 12.58‰ to C in September 2010, which were much higher than − ◦ , with the highest values observed in groundwater from Fu- 1 − 35.48‰ in JR water (Tables 1–2 and 4–5). Moreover, heavier iso- O values of the surface and groundwater samples collected in July − in July and 429–965 µScm 18 1 δ − (sample location J20, groundwater in the Fugou). Such high mineraliza- 1 − O values varied from 18 D and C in July and 22.5–24.5 ◦ δ δ 91.33‰ to 119 to 236 mV. − − Results of chemical analyses of groundwater and surface water samples are shown The total dissolved solids (TDS) represents the total mineralization (inorganic con- Signatures of all of these groundwater samples except the sample SY3 remained the The The two tributaries of Suoxu River and Dongfengqu flow into the JR in north and east The surface water samples obtained in the second sampling campaign present The in the Piper diagram (Fig. 5). In the upper stream waters (J3 and J8), SO 1385.3 mgl tion in a naturalmations environment (Petelet-Giraud of et al., groundwater 2007). generallylacustrine-alluvium The and occurs local contains in no geological evaporate; water environmentstudied therefore evaporite is it are Pleistocene for- is influenced impossible by thatThe the the deep layers source saline of groundwater theindirect (Han anthropogenic high et activities al., dissolved that 2002; ions haveover Gao, occurred content the 2008). in last can, cities few therefore, or decades. counties be along related the to river direct or of this study areafrom was found to be under oxidation conditions withtent) Eh of values water ranging dissolved and content was in well water. TDS correlated values with varied EC between 303.9 ( (surface water J3) and from 608 to 2280 µScmgou (sample J20). The waterto temperature 29.1 measured in surfacethe water varied temperature from measured 25.5 inof groundwater the in surface both waterpH campaigns showed varied (16.8 between pH 6.83 to values andconcentrations 21.3 between 7.52 of with the 7.0 surface no and water obvious andan 8.0, variation groundwater averaged during ranged whereas concentration the from of groundwater 1.2 campaigns. 3.04 to mgl DO 6.3 mgl the flood peak period.than The that levels in of location SY9,pollutant EC which passed. in is The location because latter J10, theditions, SY12 EC flood which peak and values is carrying were SY15 likely aresulting significantly were due large from lower to lower amount heavy during a precipitation of considerable during post-rain amount this con- period. of EC dilution values of in ions groundwater concentration varied location J9 and SY9 was primarily due to samples collected before rain and during to 1637 µScm flected the pollutant migration process in the river channel. The high level of EC in same during the flood periodseems and after to the be flood large period,Sample which enough indicates SY3 to that was mask the depleted aquifer the inthat seasonal lighter the isotopes isotopic after riverbank-aquifer variation the water causedand flood by may river period, rainfall. water originate possibly with indicating from more depleted a isotope mixing values. of4.2 original groundwater Main geochemical parameters Electrical conductivity (EC) (Tables 1, 2) measured in surface water varied from 541 reflect the mixture of the two channels. a wide rangemostly of negative. stable It could isotopic be due signatures. to Isotopic precipitation with composition lighter of isotope. river water was water from the shallowprecipitation. Quaternary aquifer most probably originate from present-day from topes were enriched inevaporation form river reservoirs water where in these the samples were upper collected reaches, (Fig. which 4). Zhengzhou, resulted respectively, and mostly from the resulting water sampled downstream (J10) should McDonnell, 1998). and September 2010 were plottedtion in in Fig. 4 Zhengzhou; with WMO/IAEA, the 2010)These local samples giving meteoric are accurate line well information (LML; distributed on precipita- along the the LML, input illustrating signal. that surface and ground- of concentration variations in the input such as rainfall and surface water (Kendall and 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 1 − is − 2 4 + rich 2 , July 3 1 was as − + and from dominant 1 − 3 − ) show the pro- + , whereas, Ca 1 − and HCO content due to anthro- + 2 + and Na − contents excess the World − 3 is accumulated. Chloride is the and Na ecting hydrology and water qual- − ff − 2 4 , which may be related to untreated or − dominant and is characterized as Ca-Mg- show maximum concentrations in ground- ce of NBS, 2010). To increase crop yield + − ffi 5964 5963 water type, whereas groundwater in the lower 3 and K and Cl − 3 + 2 people (Henan Provincial Bureau of Statistics, 2011). 6 10 over the lower reaches of reservoirs, with the highest con- · − 3 rich in September 2010. In contrast, the chemical composi- during the post-flood period are the same as those during the 3 in the upper reaches of Zhengzhou, and then increases by a fac- (Table 1), respectively. It is speculated that the source of SO + 1 , which is 32 times higher than the averages of the other ground- 1 . It showed most variations in Cl − 1 − 1 people, whereas the lower reaches of counties are relatively small − − 6 10 and Na · − ects of urbanization on the major ion chemistry of the JR. Concentration of ff water type. In the groundwater of location J20, the concentration of K 3 is below 30 mgl Among the dissolved solutes, NO Chloride and sodium are major electrolytes in human urine (Kirchmann and Petters- The chemical composition of groundwater at SY3 varied from Ca-Na-Cl-HCO − ees, a total sownBureau area of of Statistics 144 and 730 Henan ha, Survey and O 120 099 large animals (Henan Provincial Trends in Cl flood period. However, the concentration duringduring the the post-flood flood period period is due lower to than the that precipitation. water in Fugou County. Thesetices high in nitrate this levels region, can especially beet artificial attributed al., and to 2005; manure agricultural fertilization prac- Ma10 (Zhang et et counties al., al., growing 1996; 2009) vegetable Liu and in animals China. breeding. In Fugou 2009, County Fugou is one had of 361 000 the rural top employ- nounced e Cl tor of 4.4 inlower the reaches urban of region the of cityulation north in of July. Zhengzhou. The 4.3 It reason becomes iswith that rapidly population Zhengzhou diluted is of over a 0.5–0.8 the big city with a pop- dicators of land use (Meybeckhuman and activity Helmer, is 1989). related Chemical to alterationcially development associated the of with discharge city of and untreated intensificationeconomic sewage of development, wastes. agriculture, population Therefore, espe- growth, human and activities urbanizationof driven jointly river by result water in quality. alterations son, 1995) and are therefore concentratedriver primarily distance in profiles waste water. (Fig. The 6) concentration- for the two indicator ions (Cl 5.1 Anthropogenic sources and impactsHuman on activity surface is water one and of groundwater ity. the Water most chemistry important of factors rivers a can reflect changes in watersheds, making rivers good in- 5 Discussion reaches Zhengzhou (SY14) is Ca Cl-HCO high as 51.49 mgl water samples. Furthermore, clearof anthropogenic location inputs SY14 are and indicated J20 in (FugouHealth groundwater County) Organization where high Standard NO calculated (WHO, as 2008) N) for and drinking water Chinese (Ministry limitation of Environmental value Protection, China, (10 mgl 2002). in July to Na-Ca-HCO tion of water from otherthe wells concentrations did of not major changegroundwater ions significantly from during varied the the considerably areaand study from near period, is well but the characterized to Chulou as well. Reservoir Ca-Mg-HCO For is example, Ca second anion after HCO centration being measured in north Zhenghzou2010). during There the are flood period many (191 possibleinadequately mgl treated sources sewage of and Cl industrialthe activities. river Sodium water is during the dominant thethe cation flood dominant of period, cation varying from except 92from for to north 41 194 to mgl Zhenghzou 63 during mgl pogenic the influences post-flood during period, the varying flood period compared to the post-flood period. are the predominant ions, with49.08 concentrations ranging to from 56.17 132 mgl toresults 172 mgl from the oxidationand of JR, uncovered considering pyrite mining in inreservoir the headwater retains upstream areas river mountain water, of area the (Pang, the concentration 1994). Suoxu of Because River SO the 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , − and − O of river water (location J9 in 18 δ O of original groundwater in July 2010 in the UK (Powell et al., 1987) and up 18 1 7.54, respectively. During the post-flood D or − δ − δ or ‰) of the mixed water sample (location , − 1 5966 5965 D or − O) throughout the hydrological cycle, which did δ , 18 − δ O was found to be depleted. In the same way, the 57.80 and 18 D, is the Cl − O (mgl δ δ O signatures. 18 RW δ 18 is the Cl C δ D and GW δ D or C δ , D and − δ 100% (1) · O of water were 18 GW δ O, respectively. Mixing calculations suggest that the groundwater at SY3 in GW in Canada (Health Canada, 2008). Those results are probably caused by C is the Cl C 18 1 − s − δ − C s RW D and C content in September 2010, was also diluted. That is because the recharge by river C δ The resulting fractional contrition percentages are 60 %, 61 % and 70 % using Cl When these water sources are considered as end members to the groundwater at Assuming that groundwater at SY3 in September 2010 was a result of mixing orig- The composition of groundwater at SY3 in September 2010 can be described by The regional wells ranged from 70 to 1190 m from the river and had water with a con- The transitional well of SY3, 30 m from the river, seemed to be closely connected − = D and river water can be into the groundwater if the river water is severely polluted. SY3 in September 2010); September 2010); and that is not influenced byoriginal river groundwater end-member recharge. because Location it SY3 has in not July recharged 2010 by was theδ chosen river. as the September 2010 was composedthe of tracer approximately 60–70 employed. % This river result water, shows depending that on more than half of water contamination of f where water because river flood in September 2010 was mainly fromSY3, the it precipitation. is possiblebalance to approach estimate (Christophersen mixing and proportionsand Hooper, Mcdonnell, between 1992; 1998). the Clark waters and using Fritz, a 1997; mass- Kendall inal groundwater (GW) andassess river the water fractional (RW), contributions the of following river equation water to could the be groundwater: used to water via bank infiltration inrelatively September depleted 2010, could be characterized by lower Cl a mixture of twoand river possible water. sources, The including river water groundwater and from rainwater the sources were regional combined system, in one as river Cl the (September 2010), the stant stable isotopic signature ( not reflect seasonal variationsprecipitation. although This the illustrates river thatfrom water surface the isotope water. groundwater varied never greatly or due rarely to receivedto recharge the nearest river waternatures as and the chloride groundwater hadhydrochemistry content of similar with groundwater trends at the of SY3 stable are river. as isotope The follows. sig- During salient the pre-flood features (July of 2010), the isotope and did not include water recentlythe recharged basin); from and the (2) river transitionalposite wells, (all in locations of areas except recharge where the ground from SY3flow water in periods; was the possibly and river a was com- and(location only SY3). water water from from regional regional systems systems during during river river low high flow periods the use of a large amout of fertilizer. 5.2 Interactions between surface water andBy groundwater synthesizing various types of fielda data obtained picture in of this the study, itwater surface is wells possible water were to and provide generally groundwater categorizedcentrations into interactions and two within groups stable the based isotope basin. on values: Ground- dissolved-solids (1) con- regional wells, in areas where ground water organic fertilizers with improperthroughout proportions agricultural of regions nitrogen, of phosphorous,into Fugou. and groundwater. This potassium Potassium concentration approach (J20) hasconcentrations largely led in exceeds to the drinking losses mean water, e.g. potassium ofto 2.5 fertilizer 8 mgl mgl and income, farmers are currently decreasing the use of organic fertilizer in favor of in- 5 5 20 25 15 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | - ffi ective ff ce of NBS: 2010 Henan Statistical ffi 5968 5967 in north Zhengzhou City significantly increased in river − The authors are grateful to Major Science and Technology Program for O measurements of microliter natural water samples, Anal. Chem., 80, 287–293, 16 The concentration of Cl samples during two campaigns conducteduntreated due or to slightly discharge treated ofconcentrations waste a water. in large Nitrate amount groundwater and of tributed in potassium to show Fugou agricultural maximum practices County. crossfertilization These this and region, high animals especially breeding. levels artificial and can manure beThe at- regional wells had watertrates with that a the groundwater constant never stable or isotopic rarely signature. receiveThe This recharge illus- transitional from surface well water. infiltration of in SY3 September seemed 2010. to Fractional be contributions recharged of the by river river water water to via the bank of water contamination of river wateris can severely be polluted. into the groundwater if the river water groundwater were calculated based onbalance isotopic approach. and The chemical groundwater (SY3 data in usingcomposed September a of 2010) mass- was 60–70 approximately % river water. 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D.: The dynamic relationship Ma, J., Ding, Z., Wei, G., Zhao, H., and Huang, T.: Sources of water pollution and evolution of 5 5 30 25 20 15 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | O O 18 18 8.36 8.29 8.54 8.58 9.68 8.47 6.64 3.34 4.02 6.47 4.96 δ δ 11.52 12.07 12.58 11.93 11.61 11.24 12.37 − − − − − − − − − − − − − − − − − − D ‰‰ D ‰‰ δ δ 61.56 62.36 63.06 62.78 71.80 62.48 54.25 35.48 38.10 82.91 86.53 85.92 86.61 81.49 83.12 54.08 45.26 91.33 − − − − − − − − − − − − − − − − − − 1 1 − − mgl mgl 1 1 − − mgl mgl 1 − 1 − mgl mgl 1 − Ca K Mg Na 1 − Ca K Mg Na mgl mgl 4 1 − SO 1 4 − mgl SO mgl 3 1 − 3 1 mgl − 1 − Cl NO mgl 5972 5971 mgl 1 − Cl NO 3 1 − mgl 1 3 − MV mgl mgl 105.90 156.28 33.42 2.26 47.88 44.87 8.50 8.14 25.66 − 1 − 1 − pH DO HCO pH DO ORP HCO T C mgl ◦ T C mgl ◦ 1 1 − − Major ions and stable isotope concentrations in surface water in September 2010. Major ions and stable isotope concentrations in surface water in July 2010. µScm µScm SY20 565 23.20 7.45 3.65 137.40 183.82 58.32 BDL 76.29 50.93 8.22 15.62 42.49 SY15 532 22.80 7.39 4.02 180.20 208.38 31.24 9.98 71.06 54.31 8.28 15.10 38.85 SY12 525 22.50 7.37 4.06 167.40 186.05 20.61 BDL 84.46 56.56 8.25 14.68 35.72 SY9 604 23.00 7.41 2.57 165.20 226.98 32.67 3.31 86.01 63.16 9.91 15.90 46.33 J10 720 22.90 7.46 2.66 173.00 226.98 66.23 6.95 97.30 63.06 10.04 17.56 58.85 J9 965 22.90 7.27 1.64 45.30 241.87 73.56 2.31 191.02 62.24 10.57 15.97 109.30 NameJ3 EC J8J7 490 511 24.20 429 24.50 7.51 22.50 8.02 3.48 7.41 6.02 3.02 29.00 142.50 127.26 126.51 15.98 15.88 BDL BDL 132.67 150.33 41.32 45.35 5.16 6.91 20.90 21.52 24.23 25.46 SY20 1063 29.10 7.52 1.48 312.56 122.26 18.58 111.01 73.07 11.19 29.30 111.10 SY15 1025 27.30 7.47 1.20 331.17 114.70 23.52 92.59 76.90 10.69 27.95 105.00 SY12 1023 26.10 7.64 1.45 353.50 113.08 17.47 95.09 77.12 11.25 27.66 99.55 SY9 1637 26.50 7.69 1.97 320.01 106.48 37.41 93.32 81.10 11.02 27.23 101.60 J10 967 25.50 7.54 1.29 265.12 134.22 8.14 111.00 72.19 11.80 22.21 92.28 J9 1535 28.50 7.62 1.62 381.77 191.24 9.84 241.17 86.59 16.36 29.27 194.50 J7 951 28.10 8.51 6.30 201.49 138.47 12.69 134.45 49.51 8.79 29.60 104.70 J8 541 28.60 8.34 4.91 109.58 35.20 BDL 159.25 49.08 7.38 24.62 27.18 NameJ3 EC 600 28.60 7.97 3.38 144.93 40.46 BDL 171.64 56.17 6.49 28.25 31.63 BDL: below detection limit. Table 2. BDL: below detection limit. Table 1. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | O 18 8.15 8.39 7.54 6.72 8.76 8.42 7.63 7.54 8.15 δ − − − − − − − − − D ‰‰ δ 58.95 59.35 55.43 51.53 63.00 61.26 58.18 57.80 59.27 − − − − − − − − − 1 − mgl 1 − mgl 1 − mgl 1 − Ca K Mg Na mgl m m 1 4 − SO mgl 1 3 − mgl 5974 5973 1 − Cl NO mgl 1 3 − mgl 1 − PH DO HCO Name Approximate distance from riverJ5 Depth of well SY3SY4SY6SY7SY10J20SY14SY16 570 30 230 170 380 590 50 1190 310 28 20 38 70 25 16 14 9 9 T C mgl ◦ 1 − Major ions and stable isotope concentrations in groundwater in July 2010. The information of groundwater wells. µScm SY16 1956 17.50 6.94 2.58 569.31 186.23 39.35 144.74 156.80 0.27 78.79 126.50 SY14 2130 16.80 6.83 1.11 427.73 363.39 122.62 117.01 224.90 0.24 77.89 75.21 J20 2050 18.00 7.16 2.59 661.04 218.50 49.72 255.85 116.90 51.49 68.52 199.00 SY10 1063 17.50 7.16 0.94 367.63 106.96 BDL 97.52 138.60 1.47 29.99 50.90 SY7 1018 17.30 7.52 3.68 439.08 115.80 6.05 14.32 83.53 1.32 54.80 59.51 SY6 1370 17.70 7.13 1.80 544.38 118.04 BDL 77.86 106.70 2.36 38.13 120.90 SY4 1274 20.20 7.00 1.47 487.82 131.27 13.16 154.71 139.60 1.86 29.14 103.60 SY3 1534 17.20 7.33 0.36 417.12 264.47 9.42 150.91 147.50 4.56 25.33 152.10 NameJ5 EC 646 17.50 7.11 3.16 335.82 38.71 12.68 18.69 93.13 0.81 22.21 18.68 BDL: below detection limit. Table 4. Table 3. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | O 18 8.29 8.08 8.38 6.52 8.04 8.77 8.47 δ 10.12 − − − − − − − −

D ‰‰ δ 59.82 61.19 73.33 63.24 51.75 56.93 58.22 57.67

− − − − − − − − 1 − mgl 1 − mgl 1 − mgl 1 − Ca K Mg Na mgl 4 1 − SO mgl 3 1 − mgl

1 − Cl NO 5976 5975 Fig.1 Fig.2 mgl 3 1 − MV mgl 119.90 513.50 113.74 BDL 91.14 112.40 2.14 33.45 110.30 − 1 − PH DO ORP HCO T C mgl ◦ 1 − Major ions and stable isotope concentrations in groundwater in September 2010. Study area and relevant sampling locations. µScm J5 608 23.20 7.22 7.09 236.00 327.45 28.23 6.44 19.90 83.94 0.61 20.90 17.72 Name EC SY3SY6SY7 1317 1275 18.30 18.20 7.16 980 7.16 21.30 2.25 7.34 2.08 193.60 4.34 502.34 150.22 138.40 16.95 476.29 105.74 90.07 114.30 BDL 4.69 18.56 15.72 162.00 79.05 1.25 51.63 56.55 SY10 1070 17.90 7.16 2.49 165.60 409.31 98.90 BDL 113.66 133.90 1.42 29.33 55.56 J20 2280 17.80 7.00 1.62 154.10 632.57 251.22 58.63 285.70 154.30 50.80 74.35 194.00 SY14 1913 17.20 6.90 1.73 158.80 420.47 338.26 72.14 155.42 228.70 0.36 70.05 68.24 SY16 2040 17.40 6.89 2.95 161.30 561.87 218.74 33.31 234.50 211.00 0.31 80.81 132.30 Fig. 1. BDL: below detection limit. Table 5.

Fig.

). http://www.ngac.cn

Fig.2 Fig.1 5978 5977 Fig.3 Fig. 4 Major geological formation of the study area (data source: Monthly precipitation in Zhengzhou. Fig. 3. Fig. 2.

Fig.

July and (a)

Fig.3 Fig.3 Fig. 4

Fig. 5 Fig. 6 5980 5979 O in water collected from JRB in 18 δ D and δ

Relationships between Piper diagram of major ion chemistry for groundwater, river water and lake water in the Fig. 5. study area. Fig. 4. September 2010.

Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper |

5981 Fig. 5 Fig. Fig. 6 Major ion concentration/distance from river mouth proﬁles for chloride and sodium in the Fig. 6. main stream of the JR.