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Procedia Earth and Planetary Science 17 ( 2017 ) 726 – 729

15th Water-Rock Interaction International Symposium, WRI-15 The hydrogeochemical characteristic of mineral water associated with water-rock interaction in ,

Qian Zhanga, Xiujuan Lianga, Changlai Xiaoa,1

aKey Laboratory of Groundwater Resources and Environmentˈ Ministry of Educationˈ University. The Chaoyang District, 2519 Jiefang Street, , 130021, P. R. China.

Abstract

The mineral water in Jingyu County (Northeastern China) is an important source for bottled drinking water. In this study, we used water materials sampling from field studies during 2011-2015 to analyze the hydrogeochemistry evolution process. Isotope sampling and hydrogeochemistry analysis have been applied to prove relevant conclusions. The results showed that the water type of some springs changed from Ca-HCO3 face to Ca-Mg-HCO3 face, and the other springs kept the category with Ca-Mg- HCO3 face. The mineral water geochemical compositions originated from water-rock interaction and secondary evaporation. The recharging path of mineral water is along the southwest to the northeast based on isotopic composition analysis. ©© 20172017 Published The Authors. by Elsevier Published B.V. Thisby Elsevier is an open B.V. access article under the CC BY-NC-ND license (Peerhttp://creativecommons.org/licenses/by-nc-nd/4.0/-review under responsibility of the organizing). committee of WRI-15. Peer-review under responsibility of the organizing committee of WRI-15 Keywords: mineral water; hydrogeochemical characteristic; isotope; water-rock interaction.

1. Introduction

Water is the source of human lives, and it is indispensable to social and economic development. With the characteristics of purity and rich in great mineral and nutrition1, natural mineral water is getting more and more favor of people, the relative research is also appreciated. Numerous thermal and mineral springs are located in active volcanic regions all over the world2,3, Changbai Mountain (Northeast of China) is also a mineral water system as a result of eruptive events4. Mineral water has special hydrochemical compositions and stability dynamic characteristic, which results from long-term water-rock interaction. Jingyu County is located in northeastern China which along the central region of Changbai mountain, between 126e34Ą58ą to 126°48′38″ E longitude and 42e10Ą49ą to 42e22Ą02ą N latitude (Fig. 1(a)). The study area is characterized as having a temperate

* Corresponding author. Tel.: +86-186-2691-4139; fax:+86-0431-8850-2606. E-mail address:[email protected].

1878-5220 © 2017 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of WRI-15 doi: 10.1016/j.proeps.2016.12.184 Qian Zhang et al. / Procedia Earth and Planetary Science 17 ( 2017 ) 726 – 729 727 continental monsoon climate with significant winds during all four seasons, with an annual mean temperature being 0~2.5ć, an annual mean precipitation being 750~850 mm, an annual mean relative humidity being 73%.The multi- layer aquifer system in study area was formed after volcanic activities based on the Archeozoic metamorphic rock series in basement. According to the type of aquifer material and the condition of porosity development, the groundwater can be divided into two subtypes: pore phreatic water in loose rock mass, and basalt pore-fissured water. In order to acquire enough water materials for correlational research, field studies twice a year during 2011-2015 have been carried out. In this study, five times sampling data during June 2011, May 2012, May 2013, May 2014, 2- - July 2015 from Jingyu County were collected. Major anions including carbonate (CO3 ), bicarbonate (HCO3 ), - 2- 2+ 2+ + chloride (Cl ) and sulphate (SO4 ), and the cations including calcium (Ca ), magnesium (Mg ) and sodium (Na ), potassium (K+) were performed in the Key Laboratory of Groundwater Resources and Environment Ministry of Education)ˈJilin University. Isotopes were also analyzed in the Scientific Test Experiment Center of Jilin University, the compositions of stable isotopes (δD and δ18O) were quantified by a liquid water isotopic analyzer.

Fig. 1 (a) Location of JNCA and the distribution of 17 springs in the study area; (b) The relationship between the concentration of 3H and the sampling height vs recharging height

2. Methods and results

Due to the influence of the different initial humidity conditions and the second evaporation in the process of precipitation, make the slope of the meteoric water line difference. The intersection point of the GMWL (global meteoric water line) and the LMWL (local meteoric water line) can approximately reflect the average hydrogen and oxygen stable isotopic composition of the original water source5. The isotopic results were demonstrated in the standard of δ notation and normalized with the method of VSMOW (Vienna Standard Mean Ocean Water), which is a water standard to define the isotopic composition of fresh water. If it is determined that the groundwater recharges by precipitation, the recharging location and scope can be estimated. The stable isotopes (δD and δ18O) compositions of precipitation have altitude effect, on the basis of which aquifer recharge area and elevation can be determined. Altitude effect refers to the area where the topographic relief is large, the isotopes (δD and δ18O) compositions of precipitation reduced gradually along with the increase of the ground height. The recharge height can be described as the equation below6:

HKh (-)/GGSP  (1) 18 where H is the height of isotope’s recharging, h is the height of sampling location, δs is the concentration of δ O (or 18 Δd) of mineral water sample, δP is the concentration of δ O (or Δd) of precipitation near the sampling location, K is the height gradient of δP (-δ/100m). Furthermore, the water types of groundwater can be identified according to the concentration of major cations 2+ 2+ + + - - 2- 2- 7 (Ca , Mg , Na , K ), anions (HCO3 , Cl , SO4 , CO3 ) and TDS by plotting a Piper diagram . The chemical composition of mineral water samples changes obviously according to the diagram from Fig. 2.

728 Qian Zhang et al. / Procedia Earth and Planetary Science 17 ( 2017 ) 726 – 729

100 100

EXPLANATION EXPLANATION 1 2 2 3

- 3 - l C 4 l C C a 2+ C a 2+ 4 + 5 + 2- + 2- + 4 5 M 4 O 6 M g O S 2+ g 6 8 S 2+ 7 9 8 10 9 11 10 12 11 13 0 0 12 14 0 0 13 100 0 0 100 15 100 0 0 100 14 16 15 17 16

- 17 - 3 O 3 O C C N H 2+ S N H a + + 2+ S g 2- O a + + g 2- O + 4 2- M 3 + 4 2- K O M 3 + K O C + C

100 100 0 100100 0 0 100100 0 100 0 0 100 100 0 0 100 - 2+ Cl 2+ - Ca Ca Cl CATIONS ANIONS CATIONS ANIONS 2011-06 2015-07

Fig.2 Piper diagram to show the water types of spring-water

The source of groundwater can be inferred with the relationship between isotopic composition of sampling 18 waters and the location of LMWL. The plot of δDVSMOW versus δ OVSMOW of mineral water is shown in Fig. 3(a). Among these, GMWL is based on the regression analysis of stable isotopes (δD and δ18O) and the data are from the Global Network of Isotopes in Precipitation (GNIP). LMWL is referring to the data from Chinese Network of Isotopes in Precipitation (CHNIP), especially the part of northeast of China. LEL1, LEL2 are the Local Evaporation Lines which are regressive analysis from the isotopic composition of sampling data in 2011-06 and 2013-05, respectively. According to the composition of stable isotopes (δD and δ18O) and the sampling height, the recharging height can be decided based on the equation 1.

 

18 + + 2+ Fig. 3 (a)The plot of δDVSMOW versus δ OVSMOW of spring-water in the JNCA; (b) Gibbs diagram of TDS concentrations versus Na /(Na +Ca ) ratio for spring-water

3. Discussions

The results of hydrochemical analysis including TDS and 8 conventional ions are calculated, and the concentration of each ion is various from different year. Ca2+is a major cation with the annual average concentration of 20.75 3 - mg/dm , which accounted for 47.34% of total cations; HCO3 is a major anion with the annual average concentration of 116.56 mg/dm3, which accounted for 89.55% of total anions. The hydrochemical type of mineral waters is identified by Piper diagram in Fig. 2, and there are little changes in the water type of some springs. From 2011 to 2015, the water type of QL, LH, LY, JL2, and YL (the abbreviation of spring names) is characterized from Ca- HCO3 face to Ca-Mg-HCO3face, and the water type of the other springs keep the category with Ca-Mg-HCO3 face.

Qian Zhang et al. / Procedia Earth and Planetary Science 17 ( 2017 ) 726 – 729 729

8 It is demonstrated that the water chemical compositions have been changed in 5 years. In previous research , H2SiO3 with the concentration ranging from 25.43-42.95 mg/dm3 is a special chemical composition, and abundant in 2+ 2+ containing. The high ratios of Ca /Mg and H2SiO3 indicate they mainly originate from pyroxene (CaMgSiO6) and - 2- olivine (Mg2SiO4) in basalt, and low ratios of Cl /SO4 suggest that human activities is rarely affected. Moreover, the chemistry mechanism which controlled the mineral water geochemical compositions is distinguished to be rock dominance from the Gibbs diagram (Fig. 3(b))9. The stable isotopes (δD and δ18O) are good tracers to understand the origin and evolution history of natural water10. By detecting δD and δ18O, their average concentrations are -87.07‰ and -12.30‰, respectively. From Fig. 3(a), LEL1 and LEL2 are deviated the local meteoric water line (LMWL), which attributes to water-rock interaction and secondary evaporation11. On the other hand, the obvious groundwater evaporation is resulting from shallow groundwater depth in the study area12 The spatial distribution of isotope 3H from upstream to downstream, its concentration should be ranging from high to low, but in Fig. 1(b) the relationship between sampling height and concentration of 3H does not conform to this law. Therefore, we suggest that the mineral water in this area is from different groundwater aquifer system. The recharge source of 17 springs can be divided into three groups (distinguished by three circles in Fig. 1(b)) according to the location and the concentration of 3H. Based on the recharging height in the Fig. 1, it is demonstrated that the recharging path of mineral water is along the southwest to the northeast.

4. Conclusions

In this study, hydrogeochemistry and isotopes have been analysis to indicate the evolution process of the mineral water in Jingyu County. The water type of QL, LH, LY, JL2, and YL changed from Ca-HCO3 face to Ca-Mg-HCO3 face, and the water type of the other springs kept the category with Ca-Mg-HCO3 face. The mineral water geochemical compositions originated from pyroxene (CaMgSiO6) and olivine (Mg2SiO4) in basalt which controlled by rock dominance. Based on the variations of isotopes (δD and δ18O), the hydrogeochemical evolution also influenced by water-rock interaction and secondary evaporation. The recharging path of mineral water is along the southwest to the northeast based on isotopic composition analysis.

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