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Procedia Earth and Planetary Science 17 (2017) 534 537

15th Water-Rock Interaction International Symposium, WRI-15

An isotopic geoindicator in the hydrological cycle

Zhonghe Panga,b,1, Yanlong Konga, Jie Lia, Jiao Tiana,b
a
Key Laboratory of Shale Gas and Geoengineering, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
b
University of Chinese Academy of Sciences, Beijing, 100049, China

Abstract

This paper synthesizes the research findings on the stable isotopes (2H and 18O) of the water molecular, with respect to
applications in tracing the natural water cycle. A general purpose diagram of 2H versus 18O may serve as a geo-indicator of
various circulation processes the water is involved: hydrological, hydro-meteorological and hydro-geochemical. Equations and
explanations are provided for a total of 13 lines in the diagram that are illustrated to show the fractionation and changes of stable
isotopes when experiencing different processes: GMWL; Moisture recycling line; evaporation line, mixing lines with seawater
and andesitic water, exchange lines with H2S, CO2, silicate mineral, hydrocarbon, carbonate and clay minerals. These lines serve
as a basis in using water stable isotopes in the hydrological, hydrogeological and paleo-climate research.
2017
2017Published
The Authors. Published
by Elsevier B.V. by
ThisElsevier B.V.
is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of WRI-15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
Keywords: Hydrological cycle; stable isotope; geoindicator; 2H - 18O diagram

1. Introduction

The isotopic ratios of the chemical elements oxygen and hydrogen forming the water molecular (18O/16O and
2
H/1H, respectively) are powerful tools when used in hydrological, hydro-meteorological and hydro-geochemical
logical and climatic processes (Fig. 1). Such studies require a good understanding of the isotopic fractionation and
mixing in processes controlling the isotopic composition of different water bodies in the hydrological systems like
vapor, precipitation, surface water, groundwater and glacier ice in polar and high mountain regions.

* Corresponding author. Tel.: +86-10-82998611; fax: +86-10-62010846.

E-mail address: z.pang@mail.iggcas.ac.cn

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.2016.12.135
 Zhonghe Pang et al. / Procedia Earth and Planetary Science 17 (2017) 534 537 535

Fig. 1. Stable isotope fractionation of the water molecule in natural water cycle

Since the discovery of Global Meteoritic Water Line (GMWL1), the 2H versus 18O diagram has often used to
identify whether the water source is originated from precipitation and what atmospheric processes it has undergone.
Later on, several other atmospheric processes, such as evaporation from open surface of a water body, mixing of
different water masses, various diagenetic water-rock interactions (isotopic exchange with minerals caused by
mineral alteration) are found and generally illustrated in the 2H - 18O diagram together with the GMWL. In this
paper, we attempt to synthesize isotopic variations in major types of processes in the natural water cycle as well as
water-rock interactions that control the stable isotopic composition of the water molecules and show them all in a
single 2H versus 18O diagram. It has been found useful in learning (and teaching) and even more in practical
applications of stable isotopes.

2. The 2H - 18O diagram

Although it is difficult to exhaust all possibilities causing stable isotopic changes involved in the natural water
cycle, those found in the literature can be summarized in a diagram such as Fig.2. New ones maybe added to the
diagram later on. The behavior of stable isotopes in these 13 processes are relatively is well understood and can be
shown using evolution trend lines in a single 2H versus 18O diagram (Fig. 2). A further separation of the diagram
is convenient if a closer look at the details of the specific process is needed. Generally speaking, one can find these
lines refer to processes in the atmospheric water system, surface water system and groundwater system.

3. Atmospheric water systems

Lines 1, 2, 10 and 11 are generally used in the atmospheric water system. Among them, line 1 is the Global
Meteoric Water Line (GMWL: 2H = 818O + 10), which is the basic reference line in all of the hydrological studies.
Line 2 is the line for recycled moisture, as has been described by3. Although most of the atmospheric water is
plotted on the GMWL, some are plotted on this line. As a follow up study, several authors4 estimated the recycled
fraction in the Urumqi basin to be 8%, based on the isotope fractionation during the process of moisture recycling.
Line 11 is the paleo-meteoric water line with depleted isotopes in the precipitation occurring during the last glacial
period2,8.
Line 1: G 2 H 8G 18O  10
Line 2: G 2 H 8G 18O  d (d 10)
Line 10: G 2 H nG 18O  d (n8, G 18OG 18OGWML )
Line 11: G 2 H 8G 18O  d (d 10)
536 Zhonghe Pang et al. / Procedia Earth and Planetary Science 17 (2017) 534 537

Fig. 2. An isotopic geoindicator for the study on hydrological and water-rock interaction processes

4. Surface water systems

Line 7 is the evaporation line, which has different slopes but always smaller than that of the GMWL. Typical
slopes are 4 6, depending on the temperature and relative humidity of the region in question. Compared with the
evaporation from the surface water, evaporation from the soil always has a much smaller slope. Line 10 is
condensate line of the evaporated vapour from an open water body. In addition, during the falling process, the
evaporation may also occur, which is called sub-cloud evaporation. It is very interesting that the deuterium excess (d
= 2H - 818O) changes numerically between 1.1 and 1.2 per 1% of evaporated fraction in both humid5 and arid
regions4.
Line 7: G 2 H mG 18O  d (m8, G 18OG 18OGWML )
Line 6 is the mixing line with a volcanic vapour, using andesitic water as an example6. These waters are mainly
found in the geothermal systems associated with island-arc volcanism, e.g. the Circum-Pasific geothermal belt.
Geothermal waters are plotted along this line if they are formed by mixing of deep andesitic water and meteoric
water. In extreme cases, mixing ratio could be as high as 25% for that of andesitic water end member 7.
Line 6: G 2 Handesiticwater -20f10, G 18Oandesiticwater -10f2
Line 8 is the mixing line with sea water. Sea water close to the seashore is plotted along this line, the same as
groundwater found in a coastal aquifer that is affected by seawater intrusion.
Line 8: G 2 H seawater 0, G 18Oseawater 0

5. Groundwater systems

Water-rock interaction processes are common for groundwater. Lines 3, 4 are line for the exchanges with H2S,
CO2. Hydrogen sulphide (Line 3) can be generated in groundwaters where an organic carbon substrate is available to
support bacterial sulphate reduction, and lead to the enrichment of 2H in the groundwater because of exchange with
H2S. A negative shift in 18O (Line 4) is expected in systems with high ratios of CO 2 to water, especially in the CO2
geological sequestration8. Lines 5,9,13 are the lines for interactions with minerals at elevated temperatures, and
silicate and clay minerals, respectively. The exchange between water and silicates can increase 2H values and
 Zhonghe Pang et al. / Procedia Earth and Planetary Science 17 (2017) 534 537 537

decrease 18O values of groundwater (Line 9). Line 12 is the line for isotopic exchange with hydrocarbons. In the
coal formations, line 12 can be found due to the exchange of hydrogen with hydrocarbon. Various underground
processes may alter the isotopic composition of groundwater, which give insights into its subsurface evolution
history and geochemical reactions of groundwater with the rocks. Geothermal waters show positive 18O shifts of
varying degrees (Line 5). This is attributed to water-rock interactions usually at high temperatures. Recently, it has
been found at low temperature geothermal water in a sedimentary basin, significant oxygen shift is found 9. No effect
on 2H is evident due to the lack of H in most rock-forming minerals. While in the clay formations, the dehydration
effect, which is in fact the exchange of water isotopes, may occur, resulting in the line 13.
Line 3:
103 ln D 2 H H 2O  H 2 S (106 / TK2 )  290.498 u (103 / TK )  127.9
G 2H H O2
G 2 H H S  103 ln D 2 H H O  H S
2 2 2

Line 4:
103 ln D 18OCO2( g )  H 2O 0.0206 u (106 / TK2 )  17.9942u (103 / TK )  19.97
G OH O
18
2
G OCO18
2( g )
 103 ln D 18OCO2( g )  H 2O

6. Conclusions

In this paper, a general purpose diagram with totally 13 trend lines to illustrate stable isotopes in the water
molecular for the purpose of hydrological studies. It can be used to study the isotopic evolution of the average
meteoric water in a study area, its evolution through the surface water and groundwater systems as part of the
hydrological cycle. They are useful to trace the water origin, reveal the various processes, including hydrological,
hydro-meteorological and hydrogeochemical ones, and to quantify the mixing of different water sources. The 2H
versus 18O diagram developed in this paper can be used as a basic reference for the application of stable isotopes
for practical applications as well as learning and teaching.

Acknowledgements

This study is carried out during the teaching of isotope hydrology at the University of Chinese Academy of
Sciences over the last ten years. The support of the UCAS and students of the classes are thanked for their
discussions in the teaching process.

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