Yoshida Textbook 2001

International Hydrological Programme
Hydrogen and Oxygen Isotopes in Hydrology

-The Textbook for the Eleventh IHP Training Course in 2001-

Editor: Naohiro Yoshida

Hydrospheric Atmospheric Research Center, Nagoya University

United Nations Educational Scientific and Cultural Organization

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International Hydrological Programme

Hydrogen and Oxygen Isotopes in Hydrology
-The Textbook for the Eleventh IHP Training Course in 2001-

Editor: Naohiro Yoshida

Hydrospheric Atmospheric Research Center, Nagoya University
United Nations Educational Scientific and Cultural Organization
Prepared for the Eleventh IHP Training Course on Hydrogen and Oxygen Isotopes
in Hydrology, 9 - 22 September 2001, Nagoya, Kusatsu, Tokyo and Chiba, Japan

Working Group for IHP Training Course,
Sub-Committee for IHP,
Japan National Commission for UNESCO
Chairperson: Prof. K. Nakamura, Nagoya University
Secretary:
Mr. T. Imura, Ministry of Education, Culture, Sports, Science and
Technology
Mr. N. Kushioka, Ministry of Education, Culture, Sports, Science and
Technology
Mr. T. Katsukawa, Nagoya University
Members:
Prof. K. Takeuchi, Yamanashi University
Prof. Y. Fukushima, Research Institute for Humanity and Nature
Mr. T. Inoue, Ministry of Land, Infrastructure and Transport
Dr. A. Iseki, Japan Meteorological Agency
Dr. T. Kishii, National Research Institute for Earth Science and Disaster
Prevention
Dr. H. Ohno, National Institute for Agro-Environmental Sciences
Dr. K. Kazahaya, National Institute of Advanced Industrial Science and
Technology
Prof. N. Yoshida, Tokyo Institute of Technology
Prof. O. Matsubaya, Akita University
Prof. J. Shimada, Kumamoto University,
Prof. M. Nakawo, Research Institute for Humanity and Nature
Prof. H. Uyeda, Nagoya University
Prof. I. Tamagawa, Gifu University
Prof. E. Nakakita, Kyoto University

Published in 2002 by the Hydrospheric Atmosheric Research Center, Nagoya
University, and United Nations Educational Scientific and Cultural Organization

Printed by Nagoya University COOP
ISBN: 4-9980619-3-3
Cover: From snow to vapour; An eruption from the crator lake of Mt.
Kusatsu-Shirane in 1982.
Preface

The objective of the Training Course is to help participants to deepen their
basic knowledge on hydrological system and to develop their skills to understand
hydrological problems, which are now crucial in many countries. The course is
part of UNESCO International Hydrological Programme (IHP) and is held every
Japanese fiscal year that starts in April. The participants mainly from Asia-Pacific
regions are given a series of lectures and practical trainings for about two weeks.
Until 1996, the course was mainly focused on general hydrology and later
concentrated on specified themes such as: snow hydrology (1998), remote sensing
(1999), limnology (1999) and hydrology related to head water management
(2000).

This year, the Eleventh IHP Training Course with a theme of Hydrogen and
Oxygen Isotopes in Hydrology will be held from 9 to 22 September, 2001 at
Nagoya, Kusatsu, Tokyo and Chiba with many lectures and practicals. Hydrogen
and oxygen isotopes are used to trace water circulation in various scales in time
and space. The technique to measure distribution of isotopes and knowledge on the
meaning on water circulation must be helpful to participants to understand
hydrological problems.

The 11th course will be conducted by contributions from
professionals/experts in universities and research institutes led by Prof. Naohiro
Yoshida, Tokyo Institute of Technology. The lectures will be given by Mr. O. Abe,
Nagoya University, Dr. K. Kuraji, The University of Tokyo, Mr. N. Kurita,
Frontier Observational Research System for Global Change, Prof. M. Kusakabe,
Okayama University, Prof. O. Matsubaya, Akita University, Dr. M. Nakawo,
Research Institute for Humanity and Nature, Dr. T. Ohba, Tokyo Intistute of
Technology, Prof. H. Satake, Toyama University, Prof. J. Shimada, Kumamoto
University, Dr. A. Sugimoto, Kyoto University, Dr. S. Toyoda, Tokyo Institute of
Technology, Dr. M. Tsujimura, University of Tsukuba, Dr. H. Wushiki, Japan
International Cooperation Agency, Dr. K. Yamada, Tokyo Institute of Technology,
Dr. M. Yasuhara, National Institute of Advanced Industrial Science and
Technology, and Prof. N. Yoshida, Tokyo Institute of Technology.

The course would not have been possible to conduct without management
supports. Dr. Giuseppe Arduino and his staff in UNESCO Jakarta Office worked
for the arrangement for the participants. The IHP Training Course is under
continuous support from the Ministry of Education, Culture, Sports, Science, and
Technology.
21 August, 2001

Kenji Nakamura
Chairperson of Working Group for IHP Training Course
Director, Hydrospheric Atmospheric Research Center,
Nagoya University

Acknowledgements

I would like to take this opportunity to thank all the authors for their great
contributions to this textbook. Without their considerable efforts, this textbook
would not have been published. It was a great sorrow that Dr. A. Numaguti who
had been expected to give a lecture on AGCM had passed away in a sudden boat
accident. The editing work was done with help from Prof. Osamu Matsubaya and
Dr. Osamu Abe. Thanks are extended to Prof. Kenji Nakamura, the chairperson of
the Working Group of the IHP Training Course and the Director of the
Hydrospheric Atmospheric Research Center, Nagoya University.
Japan National Commission for UNESCO, Sub-committee for IHP led by
Prof. Takeuchi, Yamanashi University, and Working Group for IHP Training
Course supported the activity. Mr. Imura and Ms. Kushioka, Ministry of Education,
Culture, Sports, Science and Technology and Mr. Katsukawa, Nagoya University
take roles of secretariat. Local arrangements are accomplished by Ms. Junko
Banno, Mineko Kano and Saori Haga from Hydrosheric Atmospheric Research
Center, Nagoya University.

August, 2001
Naohiro Yoshida
Editor

Chairperson of Working Group for IHP Training Course

Kenji Nakamura
Director, Hydrospheric Atmospheric Research Center,
Nagoya University

List of the contributors

Chapter 1 Fundamentals of hydrogen and oxygen isotopes in hydrology
Naohiro Yoshida
Chapter 2 General feature on the hydrogen and oxygen isotopic ratios of natural water
Osamu Matsubaya
Chapter 3 Water circulation in regional scale
Atsuko Sugimoto
Chapter 4 Isotopes in snow and ice
Masayoshi Nakawo
Chapter 5 Tritium in precipitation and surface waters
Hiroshi Satake
Chapter 6 Stable isotopic composition in soil water
Maki Tsujimura
Chapter 7 Environmental isotopes in groundwaters
Masaya Yasuhara
Chapter 8 Use of environmental isotope tracers to reveal groundwater flow system
Jun Shimada
Chapter 9 Water in arid lands
Hisao Wushiki
Chapter 10 Volcanic and hydrothermal waters
Minoru Kusakabe
Chapter 11 Sampling of fluids involved in hydrothermal system
Takashi Ohba
Chapter 12 Hydrological and hydrochemical characteristics of rainfall, throughfall,
stemflow and streamwater in the University Forest in Chiba, the University of
Tokyo
Koichiro Kuraji
Chapter 13 Methods of sampling, measurement and data processing for hydrogen and
oxygen isotopic composition in rainwater
Osamu ABE
Sakae Toyoda
Keita Yamada
Naoyuki Kurita
Shigemasa Hashimoto
Ryu Uemura
N. Yoshida
Osamu ABE
Yoshida
Addresses of the contributors (alphabetical order)

O. Abe................ Graduate School of Environmental Studies, Nagoya University
........................... Email: oabe@ihas.nagoya-u.ac.jp
K. Kuraji ............ The Tokyo University Forests, The University of Tokyo
........................... Email: kuraji@uf.a.u-tokyo.ac.jp
N. Kurita ............ Frontier Observational Research System for Global Change
Email: nkurita@jamstec.go.jp
M. Kusakabe ...... Inst. for Study of the Earth's Interior, Okayama University
........................... Email: kusakabe@misasa.okayama-u.ac.jp
O. Matsubaya Research Inst. of Materials and Resources, Mining College, Akita University
........................... Email: matsub@rimr.akita-u.ac.jp
M. Nakawo......... Research Inst. for Humanity and Nature
........................... Email: nakawo@chikyu.ac.jp
T. Ohba............... Volcanic Fluid Research Center, Tokyo Inst. of Technology
........................... Email: ohba@ksvo.titech.ac.jp
H. Satake............ Dept. of Environmental Biology and Chemistry, Toyama University
........................... Email: satake@sci.toyama-u.ac.jp
J. Shimada.......... Dept. of Earth Science, Kumamoto University
........................... Email: jshimada@sci.kumamoto-u.ac.jp
A. Sugimoto....... Center for Ecological Research, Kyoto University
........................... Email: atsukos@ecology.kyoto-u.ac.jp
S. Toyoda ........... Dept. of Environmental Science and Technology, Tokyo Inst. of Technology
........................... Email: stoyoda@chemenv.titech.ac.jp
M. Tsujimura...... Hydrology Lab., Inst. of Geoscience, University of Tsukuba
........................... Email: mktsuji@atm.geo.tsukuba.ac.jp
H. Wushiki ......... Japan International Cooperation Agency
........................... Email: wushiki@huca.go.jp
K. Yamada.......... Dept. of Environmental Science and Technology, Tokyo Inst. of Technology
........................... Email: kyamada@chemenv.titech.ac.jp
M. Yasuhara ....... National Inst. of Advanced Industrial Science and Technology
........................... Email: masaya-yasuhara@aist.go.jp
N. Yoshida Frontier Collaborative Research Center, Dept. of Environmental Science and
Technology, Tokyo Inst. of Technology
.......................... Email: naoyoshi@depe.titech.ac.jp
..........
Chemislr, and LnyineerinyTokyo Inst. of Technology
p
Tokyo Inst. of Technology pel. oI LnVironmenlaI Chemislr, and
Contents

I Textbook

1 Fundamentals of hydrogen and oxygen isotopes in hydrology ............... 1
1.1 Introduction ......................................................................................... 1
1.2 Stable isotopes and radioisotopes of light elements............................ 1
Natural abundance of isotopes
Isotopes, isotopomers, and delta notation
Hydrogen, oxygen and some other isotopes, and their standards
in hydrological studies
1.3 Fractionation of isotopes ..................................................................... 4
Equilibrium fractionation of stable isotopes
Kinetic fractionation of stable isotopes
Decay of radioisotopes
1.4 Determination of stable isotope abundance ........................................ 7
Sampling and storage of water samples
Mass spectrometric analysis
The other analytical methods including optical methods
Reference, Textbooks and Handbooks for further reading related to
Isotope Hydrology........................................................................................ 8

2 General features on the hydrogen and oxygen isotopic ratios of
natural water ..............................................................................................
2.1 Introduction .........................................................................................
2.2 Seawater ..............................................................................................
2.3 Meteoric water.....................................................................................
2.4 Meteoric precipitation .........................................................................
General features
Isotopic fractionation in precipitation process
Isotopic fractionation on source vapor
Global features
2.5 Ice caps................................................................................................
2.6 Surface water and groundwater...........................................................
River water
Discharge to river
Lake water
Groundwater and soil water

3 Water circulation in regional scale ............................................................
3.1 Precipitation process in the atmosphere..............................................
Could type and isotopic composition of precipitation
Isotopic compositions of cloud droplets and precipitation
particles in an ascending air parcel
Other factors controlling the isotopic composition of precipitation
Spatial and temporal variations in the isotopic compositions of
precipitation
3.2 Water cycle in an ecosystem ...............................................................
Fate of rainwater enter into an ecosystem
Water uptake by plants

4 Isotopes in Snow and Ice.............................................................................
4.1 Introduction .........................................................................................
4.2 Fractionation in snow metamorphism.................................................
Snow metamorphism
Isotopic change during grain coarsening
4.3 Isotope data in ice cores ......................................................................
4.4 Concluding remarks ............................................................................

5 Tritium in precipitation and surface waters .............................................
5.1 Measurement of tritium.......................................................................
5.2 Tritium in precipitation........................................................................
5.3 Tritium in river and ground water .......................................................

6 Stable Isotopic Composition in Soil Water ...............................................
6.1 Introduction .........................................................................................
Fundamentals of rainfall-runoff processes in headwater
catchment
Physical processes of soil water movement
6.2 Soil water extraction techniques .........................................................
Suction method
Centrifugation method
Distillation method
6.3 Processes leading to isotopic variations in soil water .........................

Meteorological inputs
Evaporation
Percolation, groundwater recharge and runoff
6.4 Future directions..................................................................................

7 Environmental isotopes in groundwaters..................................................
7.1 Tracing groundwater with D and O.....................................................
Where, when, and how groundwater is recharged?
Groundwater mixing
Palaeo-groundwaters
7.2 Groundwater dating with
3
H ...............................................................
Natural and man-made
3
H
3
H as a short-term age indicator

8 Use of environmental isotope tracers to reveal groundwater flow
system..........................................................................................................
8.1 Introduction .........................................................................................
8.2 Tracing of groundwater flow in the bedrock by means of
environmental tritium..........................................................................
Hydrological case study of a small granite island
Groundwater flow around the crystalline bedrock tunnel
8.3 Groundwater flow in alluvial and diluvial aquifers revealed by
environmental isotopes ........................................................................
Recharge origin of the groundwater in Kurobe alluvial fan
The residence time analysis of an unconfined groundwater in the
Musashino upland

9 Water in Arid Region..................................................................................
9.1 Introduction .........................................................................................
9.2 Arid Region: Global Distribution and Cause ......................................
9.3 Precipitation in the Arid Region..........................................................
9.4
18
O and Deuterium (D) Contents of the Meteoric Water and Their
Characteristics. ....................................................................................
9.5 Some Case Studies ..............................................................................
South Arabia
Tarim Basin in Chinese Central Asia
9.6 Conclusion and Future Prospect..........................................................

10 Hot spring, Geothermal, Volcanic and Magmatic Waters.....................
10.1 Introduction .......................................................................................
10.2 Hot spring and geothermal waters.....................................................
Hydrogen and oxygen isotopic compositions
Subsurface evaporation
Oxygen isotopic shift
10.3 Magmatic and volcanic waters..........................................................
D value of hydrogen in the mantle
Primary magmatic water
High Temperature Volcanic Gases from arc volcanoes

11 Sampling of fluids involved in hydrothermal system.............................
11.1 Volcanic gas.......................................................................................
Property of volcanic gas
Apparatus for the sampling
Sampling and Measurements
11.2 Geothermal fluid................................................................................
Property of geothermal fluid
Apparatus of the sampling
Sampling and Measurements
11.3 Crater lake water................................................................................
Property of active crater lake water
Measurements
11.4 Hot spring water ................................................................................
Property of hot spring water
Measurements

12 Hydrological and hydrochemical characteristics of rainfall,
throughfall, stemflow and streamwater in the University Forest in
Chiba, the University of Tokyo..................................................................
12.1 Introduction and site description.......................................................
General introduction of the University Forest in Chiba
Fukuroyama-sawa Experimental Watershed
Do-sawa Experimental Watershed
Shinta Micrometeorological Observation Field
12.2 Rainfall characteristics ......................................................................
12.3 Throughfall and stemflow in Japanese Cedar and Cypress Forest....

Long-term monitoring of throughfall and stemflow
Spatial distribution of throughfall
Factors affecting stemflow volume and chemistry
12.4 Streamwater.......................................................................................
Water balance and hydrological characteristics
Effect of logging on streamflow and stream water chemistry

13 Methods of sampling, measurements and data acquisition for
hydrogen and oxygen isotopic composition in rainwater .......................
13.1 Introduction .......................................................................................
13.2 Sampling............................................................................................
Technical Procedure for cumulative sampling of precipitation for
isotopic analyses
An example for simulating evaporation-condensation and
freezing processes by laboratory experiment
An example for simulating freezing processes by laboratory
experiment
13.3 Measurement .....................................................................................
Principle of mass spectrometry
Analytical methods for hydrogen and oxygen isotopes
H
3
factor
13.4 Data processing .................................................................................
How to convert raw data to the delta value

II Outline of the Training Course in 2001....................................................

III Past Activities of the IHP Training Course ............................................

Part I

Textbook
Fundamentals of hydrogen and oxygen isotopes in hydrology
1
Chapter 1


1.1 Introduction

The Earth is called as a water planet because water is abundant in all phases on
it. Water is distributed in various reservoirs; oceans, ice caps, groundwater, fresh water
lakes, saline lakes and inland seas, the atmosphere, and the rivers in the order of their
sizes. The hydrogen and oxygen isotopes of water are variable among reservoirs in
time and space. The water exchanges among reservoirs by changing its isotopic
compositions through equilibrium and/or kinetic processes. Hence, the origin and the
circulation of water can be traced by the hydrogen and oxygen isotope abundance.
Stable isotopes of hydrogen and oxygen, and tritium have been used to trace
water circulation in various scale in time and space. They have been found to be good
tracers to understand the hydrological system. This chapter includes methods of
sampling, determination, data analysis, and transport models of isotopes in seawater,
water vapour, precipitation water, snow, ice, surface water, soil water, ground water,
and volcanic and hydrothermal water. The main aim of this textbook is to help readers
about the basic knowledge of hydrological systems and their sensitivity to climatic
changes, as well as solving current global environmental problems. Participants can get
comprehensive idea of the application of hydrogen and oxygen isotopes in hydrology
by practice to collect various kinds of hydrological samples, determine their isotope
ratios, and analyse their data by themselves. This chapter describes the fundamentals of
hydrogen and oxygen isotopes to be used in the hydrological studies.

1.2 Stable isotopes and radioisotopes of light elements

1.2.1 Natural abundance of isotopes

A nuclide of an element is mainly composed of protons and neutrons. It is defined
by the number of protons (Z) and that of neutrons (N). The total number of protons and
neutrons is called mass number (A). A nuclide is expressed in the form of
A
Z
X or
A
X
Chapter 1
2
where Z defines the element X.
2
H has another name, deuterium, and is often denoted
as D. Isotopes of an element are defined as nuclides which contain different number of
neutrons and thus different mass numbers in an element. Nuclides with too many or
very few neutrons in comparison with protons are unstable and decay (radioisotopes),
whereas those with moderate numbers of neutrons are stable and do not decay (stable
isotopes). Until now, ca. 270 stable isotopes and over 1700 radioisotopes have been
identified. The natural abundance of stable isotopes in some typical bioelements is
shown in Table 1. In comparison with stable isotopes, the natural abundance of
radioisotopes is extremely low in the atomic abundance range of 10
-17
for tritium,
3
H
(or T), and 10
-12
for
14
C.

Table 1.1 Natural abundance of stable isotopes of typical bioelements in atomic
percentage.

H C N O S
H 99.9844
12
C 98.89
14
N 99.635
16
O 99.763
32
S 95.02
D 0.0156
13
C 1.11
15
N 0.365
17
O 0.0375
33
S 0.75

18
O 0.1995
34
S 4.21

36
S 0.02

1.2.2 Isotopes, isotopomers, and delta notation

Stable isotopes and radioisotopes of environmental materials have been used to
trace their cycles in the atmosphere, the oceans, the terrestrial environment and the
biosphere. Researchers are developing proxies from single isotope analysis to
multi-isotope tracer analysis. Water is one of the molecules which have been
investigated for their isotopic abundance from the beginning of the isotope studies. As
will be shown in the following chapters, the parameter, deuterium excess, the intercept
found in the plot between deuterium versus
18
O in the meteoric water, is a good
example of such parameters generated from the combination of multi isotopes within a
molecule. Here I would like to define the term, isotopomer as an isotope-containing
molecule. A number of isotopomers are expected within a molecular species with the
combination of isotopes of multi elements composing the molecular species. In the
case of water molecule, there are 4 significantly abundant isotopomers in the
environment; H
2
16
O, HD
16
O, H
2
17
O, and H
2
18
O.
Since the variation in the naturally occurring isotopes is quite small, the stable
isotope ratios are expressed by the permil deviation from standard materials. Isotope
3
ratio is defined by the notation as

X X/X)
sample
/(X/X)
std
1) x 1000 (permil) (1-1)

where X is a heavier isotope and X is the light most one, the sample means sample
water and std denotes the standard water.

1.2.3 Hydrogen, oxygen and some other isotopes, and their standards in
hydrological studies

Expressions of hydrogen and oxygen isotope ratios, for example, are as follows;

D D/H)
sample
/(D/H)
std
1) x 1000 (permil) (1-2)

18
O
18
O /
16
O)
sample
/(
18
O /
16
O)
std
1) x 1000 (permil) (1-3)

The standards for hydrogen and oxygen stable isotopes are listed in Table 2
together with those for several other isotopes of lighter elements of interest in
hydrological studies. The standard for hydrogen and oxygen stable isotopes is
VSMOW (Vienna Standard Mean Ocean Water) which is maintained, distributed, and
calibrated with great care by the authorities of the Section of Isotope Hydrology,
International Atomic Energy Agency (IAEA) in Vienna. Lippmann et al. (1999)
reported the results of the latest inter-laboratory calibration of stable hydrogen and
oxygen isotope ratios in water standards.

Table 1.2 Standards for stable isotopes of lighter elements of hydrological interest.

Isotope Standard Relative abundance (Ratio)
2
H VSMOW 1.5575 x 10
-4
(
2
H/
1
H)
3
He Air He 1.3 x 10
-6
(
3
He/
4
He)
6
Li L-SVEC 8.32 x 10
-2
(
6
Li/
7
Li)
11
B NBS 951 4.04362 (
11
B/
10
B)
13
C VPDB 1.1237 x 10
-2
(
13
C/
12
C)
15
N Air N2 3.663 x 10
-3
(
15
N/
14
N)
18
O VSMOW 2.0052 x 10
-3
(
18
O/
16
O)
34
S CDT 4.5005 x 10
-2
(
34
S/
32
S)
37
Cl SMOC 3.24 x 10
-1
(
37
Cl/
35
Cl)
isolopes are Iisled in JabIeJ.2
2
Chapter 1
4
1.3 Fractionation of isotopes

1.3.1 Equilibrium fractionation of stable isotopes

The hydrogen and oxygen isotopes of water varies among reservoirs in time and
space because of the fact that fractionation of isotopes occurs in the natural
environment. Isotope fractionation is accompanied by variety of processes, such as,
phase change, transportation, diffusion, reduction, oxidation, chemical reaction, and
biological metamorphism. The details of isotope fractionation accompanied by various
processes will be shown in the following chapters. Here, the fundamentals of isotope
fractionation are discussed.
Isotope fractionation factor of an equilibrium process A = B is defined as follows;

= (X/X)
A
/(X/X)
B
(1-4)

where is an isotope fractionation factor. Good examples of such equilibrium
processes for hydrogen and oxygen isotopes are as follows;

HDO
liq.
+H
2
O
vap.
= H
2
O
liq.
+ HDO
vap.
(1-5)
H
2
18
O + 1/2 C
16
O
2
= H
2
16
O + 1/2 C
18
O
2
(1-6)

where liq. and vap. denote liquid and vapour phase, respectively. These are equilibrium
isotope exchange reactions between different phases and different molecules,
respectively. The equilibrium constant for each reaction is identical with isotope
fractionation factor, so that it mainly depends on the temperature.

)
= (D/H)
vap.
/ (D/H)
liq.
(1-7)
)
= (
18
O/
16
O)
CO2
/(
18
O/
16
O)
H2O
(1-8)

The values are mostly close to unity, so that it is expressed quite often as
10
3
ln . The example of such expression for
)
is as follows;

here + is an isolope Iraclionalion Iaclor. Cood exampIes oI such equiIibrium
5
10
3
ln
(15)
10
3
ln(
(D/ H)
vap
(D/H)
liq
)

=
10
3
ln
1
vap
10
3
1
liq
10
3

vap

liq
(1-9)

Care should be taken for the approximation in eq. (1-9) that holds small values,
e.g., less than 15 . For instance, the absolute value of
(1-8)
is 1.0412 at 25 degree
C and cannot be approximated by the difference in delta values.

1.3.2 Kinetic fractionation of stable isotopes

Isotope fractionation factor of a unidirectional kinetic process, such as
evaporation, chemical dissociation reactions, biologically mediated reactions, and
diffusion is defined as follows;

k
= k
X
/k
X
(1-10)

where k
X
is a reaction rate of a molecule of interest which contains a heavier isotope,
and k
X
that of the lighter most isotopomer. Lighter isotope is found to be enriched in
the product of the reaction, whereas, heavier isotope is being enriched in the reactant
that is unreacted in the course of reactions. This means most of the
k
values are less
than unity, in other words, the reaction rate of a heavier isotopomer is less than that of
the light most one. Most deviations from simple equilibrium processes can be
quantitatively interpreted as a result of the kinetic isotope fractionation which generates
from the difference in the reaction rates of isotopomers. The variety of kinetic
fractionation will be shown in the following chapters.
Water changes its isotopic compositions through equilibrium and/or kinetic
processes during circulation from reservoir to reservoir. The origin and the circulation
of water should be traced by taking into account of the hydrogen and oxygen isotope
fractionation.

1.3.3 Decay of radioisotopes

vap

liq

Lq.
( )
and cannot be approximated by the difference in delta values.
is J.04J2 al 25
Chapter 1
6
Radioisotopes undergo spontaneous transformations that are accompanied by the
emission of particles and of radiant energy. Unstable isotopes of the hydrological
interest decays by emitting a negatively charged beta particle (negatron) and neutrinos
from the nucleus, involving the emission of radiant energy in the form of gamma rays.
3
H and
14
C, for example, decay,

3
H
3
He + |
-
(1-11)
14
C
14
N + |
-
(1-12)

The decay rate of radioisotopes is proportional to the number of radioisotopes (N)
present at that instant and thus,

-dN/dt = N (1-13)

where is decay constant. Integration of this equation provides the number of
radioisotopes at the time t,

ln N ln N
0
= - t (1-14)
N = N
0
e
- t
(1-15)

The half life (T
1/2
) is defined as the time required for one-half of a given
number of a radioisotope to decay and by substitution we obtain,

T
1/2
= ln 2 / = 0.693/ (1-16)

Half lives of the several radioisotopes of hydrological interest are listed in Table
1-3. All of these isotopes are naturally produced by cosmic radiation and thus they are
called cosmogenic nuclides and decay by |
-
decay. These cosmogenic nuclides are
contaminated with the anthropogenic emission, such as atomic bomb test and nuclear
reactors, so that it can be used as a tracer of water cycle in addition to the natural dating
of water.

= 0.693/
7
Table 1.3 Several cosmogenic radioisotopes of hydrological interest.

Isotope Half-life (yrs) decay mode
3
H 12.43
-
14
C 5.73 x 10
3

-

36
Cl 3.01 x 10
5

-

39
Ar 269
-

81
Kr 2.1 x 10
5
ec
129
I 1.6 x 10
7

-

1.4 Determination of stable isotope abundance

1.4.1 Sampling and storage of water samples

As the phase change of water is accompanied by the large isotopic fractionation,
great care should be taken during sampling and storage of water samples. The
complete details of the necessary care and sampling procedures will be described in
practice chapters 11 through 13. The participants will experience how to take samples
and store them before analysis without contamination and further fractionation of
water isotopes by themselves.

1.4.2 Mass spectrometric analysis

Isotope ratios of hydrogen and oxygen have been determined mainly by the Nier
type mass spectrometer for water isotope analysis in 1950s. Since then, the principles
of the instruments have not been greatly changed except for the hardware and software
according to the electric and electronic progress. The mass spectrometer is composed
of ionising chamber where sample gas is introduced, ionised and accelerated by high
voltage, the magnetic analyser tube where the ions are bent depending on their mass
and separated, and the detector where ion currents are transformed into electron
currents and amplified. The details of the present day set up and the procedure will be
described in chapter 13.
Samples should be prepared in the gaseous form ready for the analysis on mass
spectrometer. In older days and seldom even at present, water is reduced by uranium,
zinc, magnesium, chromium, and so on to hydrogen gas by the vacuum system.
Thanks to the platinum catalysis, water is equilibrated with hydrogen gas in an isotope
Chaplers JJ
Chapter 1
8
exchange reaction between water and hydrogen at controlled temperature. The
hydrogen isotope ratio of water is determined by calibration with working standard
waters equilibrated with hydrogen gas which is actually determined on a mass
spectrometer.
The most frequently used method for the determination of oxygen isotope ratio of
water involves isotope exchange reaction which was shown in eq. (1-6). The
convenient and precise off-line method has been described by Yoshida and Mizutani
(1986). There are several other direct methods for the determination of oxygen isotope
ratio of water. Water is decomposed into oxygen gas through reaction with fluorinated
reactive gases like BrF
5
.
The present-day routine determinations are being done by online system
involving exchange equilibrium reaction being connected directly to a mass
spectrometer in most laboratories.

1.4.3 The other analytical methods including optical methods

There have been several other methods proposed for the determinations of the
hydrogen and oxygen isotope ratios of water in addition to the methods described in
the last section. Water vapour is directly introduced into a mass spectrometer with
special care for avoiding condensation. In addition to the mass spectrometric method,
optical analysis methods have been proposed and checked recently. Some optical
method of high resolution molecular spectroscopy such as tunable diode laser
absorption spectroscopy (TDLAS), Fourier transform infrared spectroscopy (FTIR) are
feasible and have been investigated and would be the alternative methods of mass
spectrometry in the future.

References, Textbooks and Handbooks for further reading related to
Isotope Hydrology

Clark, I. D. & P. Fritz, Environmental Isotopes in Hydrogeology, 328 pp., Lewis
Publishers, 1997.
Faure, G, Principles of Isotope Geology, John Wiley & Sons, 589 pp., 1977.
Fritz, P. & J. Ch. Fontes Eds., Handbook of Environmental Isotope Geochemistry
Vol.1, Elsevier, 545 pp., 1980.
Lq.
9
Gat, J. R. & Gonfiantini, R. Eds., Stable Isotope Hydrology, IAEA, 339 pp., 1981.
Griffiths, H. Ed., Stable Isotopes, integration of biological, ecological and
geochemical prcesses, BIOS Scientific Publishers Limited, 438pp., 1998.
Hoefs, J., Stable Isotope Geochemistry, Springer, 201 pp., 1997.
Kendall, Carol & Jeffrey J. McDonnell, Isotope Tracers in Catchment Hydrology,
Elsevier, 839 pp., 1998.
Lajtha, K. & R. H. Michener, Stable Isotopes in Ecology and Environmental Science,
Blackwell Scientific Publ., 316pp., 1994.
Lippmann, J., M. Groening, and K. Rozanski, 2
nd
interlaboratory comparison for
deuterium and oxygen-18 analysis of water samples, Report prepared by Isotope
Hydrology Laboratory, Agencys Laboratories Seibersdorf, International Atomic
Energy Agency, Vieenna, July 1999, 32 pp., 1999.
Mook, W.G. ed., A series of six volumes on Environmental Isotopes in the
Hydrological Cycle: Principles and Applications, the IAEA and UNESCO, available
at the website of the IAEA;
http://www.iaea.org/programmes/ripc/ih/volumes/volumes.htm , 2001:
Volume I: Introduction: Theory, Methods, Review (W. Mook)
Volume II: Atmospheric Water (J. Gat)
Volume III: Surface Water (K. Rozanski, K. Froehlich, W. G. Mook)
Volume IV: Groundwater: Saturated and Unsaturated Zone (M. Geyh)
Volume V: Man's Impact on Groundwater Systems (K.-P. Seiler)
Volume VI: Modelling (Y. Yurtsever ed.)
Yoshida, N. and Y. Mizutani, Preparation of carbon dioxide for oxygen-18
determination of water by use of a plastic syringe., Anal. Chem., 58, 1273 1275,
1986.
General features on the hydrogen and oxygen isotopic ratios of natural water
11
Chapter 2

General features on the hydrogen and oxygen isotopic ratios of
natural water

2.1 Introduction

Natural water, in general, means various kinds of water in nature, that comprises
mainly sea water, ice cap, ground water, and surface water (lake and river). Although
the term of natural water is not strictly defined, meteoric precipitation (rain, and snow),
atmospheric moisture, geothermal water, water in soil, and perhaps water in plant are
also included. Amounts of these waters are shown in Table 1.
Atmospheric moisture and meteoric precipitation are less abundant in the natural
water, nevertheless they play an important role in the water circulation on surface of
the earth. And such water circulation processes regulate hydrogen and oxygen isotopic
ratios of the natural water. One of estimation about the water circulation on the surface
is schematically shown in Fig. 2.1, though little different estimations are also presented
(e.g. Nakao, 1998). The sum of annual evaporation from both of ocean and land
(44610
15
kg/yr) is balanced with sum of annual precipitation on ocean and land, and it
is about 34 times larger than the amount of atmospheric moisture. Therefore, the mean
residence time of atmospheric moisture is about 0.029 years or 11 days.

2.J
Chapter 2
12
Table 2.1 Amounts of natural waters in different reservoirs (after Mason and Moore,
1982, partly modified)

Mass (kg)
Seawater 1.410
21

Icecaps 2.910
19

Groundwater 8.410
18

Lake water 2.410
17

Atmospheric moisture 1.310
16

River water 1.310
15

The difference between annual amounts of precipitation and evaporation on land
is balanced with the transport of moisture from ocean to land as precipitation, and
reversely with the river discharge to ocean. The annual river discharge (3610
15
kg/yr,
Fig. 2.1) is about 15% of the surface water (24010
15
kg). As explained in the
following section (2.6.2 and 6.1.1), most of the river water flows out from groundwater
reservoirs, and a part of the groundwater (8,40010
15
kg) may be only involved in the
discharge process at shallow part. Therefore, the residence time of groundwater
involved in the discharge process is shorter than the ratio between the groundwater and
the river discharge (8400/36=230 years), and may be 100 years or less. The river
discharge is about one-third of the precipitation on land. However, this ratio varies
largely in individual areas and is still controversial to explain water balance in a
catchment area.
Since beginning of stable isotopic studies in the 1950s, hydrogen and oxygen
isotopic studies have been extensively performed for the natural water. The results in
the earlier two decades are well reviewed by Ferronsky and Polyakov (1982, originally
1975) and also Fritz and Fontes (1980, 1986). In Kendall and McDonnell (1998), the
recent studies are presented. Lots of technical reports and books about this subject are
also pulished by the International Atomic Energy Agency (IAEA), Vienna.

13

Ppt
99
Ev
63
Ppt
347
Ev
383
Atmospher
( 13 )
36
Land
Ocean
( 1,400,000 )
Dr
36
( 240 )

Fig. 2.1 Water circulation on surface of the earth (after Turekian, 1969). Where : Ev,
Ppt, and Dr stand for evaporation, precipitation and river discharge,
respectively, numbers with arrows denote annual rates of water
transfer(10
15
kg/yr) and the numbers in parentheses display amounts of water
(10
15
kg).

2.2 Seawater

Homogeneity of seawater in oceans is well known from its constant salinity and
chemical composition. Hydrogen and oxygen isotopic ratios of them are also quite
constant, i.e. D and
18
O are almost 0, and vary only within 5 in D and 0.5 in
18
O, except for two particular cases (e.g. Ferronsky and Brezgunov, 1989). One
exception is dilution by fresh water such as river water at coasts and meltwater from
icecaps at high latitude areas. For instance, seawater of the Baltic Sea has D as low as
50, as a result of 80% dilution (Friedman et al., 1964). Another exception is
evaporation of seawater that result in rise in D and
18
O. In such case, the salinity of
seawater also increases, and thus a linear correlation is observed between the isotopic
ratios and the salinity. These changes are steadily observed at inland seas such as the
Chapter 2
14
Mediterranean Sea, the Red Sea and so on, and the extent of increasing reaches up to
15 in D, 3 in
18
O and 5 in salinity (Anati and Gat, 1989).
The value of 0 for D and
18
O for seawater represents SMOW is chosen as the
standard. Actual (absolute) isotopic ratios (see 1.1.1) must be fixed through some
processes during the earths history. In the case of oxygen, the largest oxygen reservoir
is silicates in the mantle, of which
18
O is in a range of +5.5 to +6.0. This oxygen of
mantle silicate had been divided into two parts, oceans and the continents, through
their formation processes, and consequently, heavier oxygen isotopes were enriched in
the continent sides, of which
18
O ranges from +10 to +15, while depleted in the
oceans. At the present, the oceans may be the largest reservoir in the earth for
hydrogen. In the early time of the earth formation, however, huge amount of H
2
O (H
2
)
had existed on the earth, and almost all of such H
2
O (H
2
) had lost, and the present sea
had been formed by a quite small residue of those water. Therefore, the process
controlling the isotopic ratio of hydrogen in the present seawater is difficult to be
estimated.
Circulation of seawater has been studied by means of
3
H and
14
C-dating method.
Large flows in the global scale have been found at deep sea, and the time of the
circulation is about several thousand years.

2.3 Meteoric water

Although the term meteoric water is used in rather diverse meaning, it may be
widely used as defined by White (1957), i.e. the term meteoric applies to water that
was recently involved in atmospheric circulation. If so, the meteoric water includes
rain (snow), atmospheric moisture, icecap, lake and river waters, groundwater (perhaps
at rather shallow part), soil water, plant water and many others without regard to its
existing form.
Since the beginning of stable isotopic studies, many observed results have been
reported about meteoric water. In those observation, two global trends were pointed out
by Craig (1961) and Dansgaard (1964). Craig (1961) found a linear correlation
between D and
18
O of meteoric water and presented a relationship with the equation,
i.e.

D = 8
18
O + 10 (2-1)

This equation is often called as Craigs meteoric relationship (or line). This
15
relationship is observed throughout the world, and the D and
18
O are higher in lower
latitudes and contrarily lower in higher latitudes as shown schematically in Fig. 2.2.
Dansgaard (1964) represented the worldwide character of D and
18
O of
meteoric water as correlation to annual mean surface temperature, i.e.

D = 5.6t 100 (2-2)
18
O = 0.695t 13.6 (2-3)

Fig. 2.2 Worldwide relationship of D and
18
O of meteoric water (after Craig, 1961,
modified).

-500
-300
-100
-60 -40 -20 0

8
O,
D,
Japan
30N
45N
Greenland
Coast
Antarctica
Inland
D=8
18
O+10
Chapter 2
16

Fig. 2.3 Worldwide relationship between
D or
18
O and annual mean surface
temperature (after Dansgaard, 1964, modified).

where t stands for annual mean temperatures at the surface. The regional features are
schematically shown in Fig. 2.3. These relationships are evident in high latitudes
(higher than 60 of both of northern and southern hemispheres), but not in middle and
low latitudes, where the annual mean temperatures are higher than 10C.
The relationships by Craig and Dansgaard should be explained by isotopic
fractionation processes in the global water circulation through the atmosphere.
However, even now, these two relationships have not yet been explained completely.

2.4 Meteoric precipitation

2.4.1 General features

In this section, first, some examples are shown about time variation in one rainfall,
fluctuation among individual rainfalls (or daily precipitation), seasonal variation, and
17
fluctuation in annual mean values. These examples were observed by the present
author at Akita (3944N, 14009E, P1 in Fig. 2.13), Japan. Although such kind of
features varies in individual regions reflecting the climatic and meteorologic conditions
in each regions, such variations are caused by difference in combination and/or
contribution of several fundamental factors as mentioned in the next section (2.4.2),
and these examples are helpful to understand characters in other regions.

(a) Time variations in a series of precipitation
Figure 2.4 shows variations in D of rainwater from the beginning to the end of
precipitation (a) and the relationship between D and
18
O (b). The total amount of this
rainfall is 85 mm for about 17 hours. The amount of rainfall for every hour is also
shown in the figure. During this rainfall, the D and
18
O change largely from 25 to
108 and from 2.9 to 14.7 , respectively. These large variations are caused by
isotopic fractionation in evaporation and condensation in cloud forming process as
well as rain falling process (see 2.4.2). In general, the extent of changes in the isotopic
ratios of one serial precipitation are various, and range from as large as the above case
to almost no change.
The relationship between D and
18
O is nearly consistence with the Craigs
meteoric line. However, slightly different relationships are observed in some part of the
series, for instance Nos. 3 ~ 7, Nos. 9 ~ 11, and Nos. 14 ~ 17, depending on differences
of rain forming processes and effect of evaporation of falling rain drops.
Chapter 2
18

21.5
24.8
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
D
ppt
mm/hr
Hour
a
0 6 12 18 24
0
5
10
-120
-110
-100
-90
-80
-70
-60
-50
-40
-30
-20

-120
-100
-80
-60
-40
-20
-16 -14 -12 -10 -8 -6 -4 -2
11
3
12
4
10
13
5
2
15
14
9
6
7
1
8
16
17 b
D=8
18
O+10

18
O,
D,

Fig. 2.4 Time variations in D of a serial precipitation as well as its intensity (a) and
its relationship of D and
18
O (b).
19
(b) Mean value of a serial precipitation
The isotopic ratios of total precipitation collected from the beginning to the end
show average values of a serial precipitation. Those average values largely vary one
by one. As shown in Fig. 2.5, for example, such averages of D for serial precipitations
in March, 1987 at Akita are in a wide range from nearly 0 to 110 .

(c) Seasonal variations
If all precipitations are collected together for one month, their isotopic ratios show
seasonal characters of meteorological condition. In Fig. 2.6, seasonal variations in D
and
18
O of monthly collected precipitation from 1991 to 95 are shown. In the case at
Akita, a certain variety is observed among these five years, and such a variety is
common in other years. However, a bimodal change in one year is obscurely found.
The D and
18
O both decrease during January ~ March and June ~ August, and
contrarily increase during April ~ May and September ~ October. The lowering during
January ~ March is more remarkable in
18
O than in D. These seasonal variations are
controlled by difference in the contribution of two factors causing isotopic
fractionation, one of which is condensation process forming cloud as well as growing
process of rain drop (snow), and the other is evaporation process of original vapor.

Fig. 2.5 D of rain (or snow) of individual precipitations in March, 1987, at Akita.

-150
-120
-90
-60
-30
0
-4 1 6 11 16 21 26 31
March, 1987
D

sho aVeraye VaIues oI a seriaI precipilalion. Jhose aVeraye VaIues IaryeI, Var, one
oI monhlI, coIIecled precipilalion Irom J99J loJ995 are shon In lhe case al
Chapter 2
20
This difference is obvious in the relationship of D and
18
O. Fig. 2.7 shows the
relationship for about 5 years averages of each month. Two different relationships are
distinguished between winter season (Nov. ~ Feb.) and the other season (Apr. ~ Sep.).
This difference is due to the difference in vapor sources, i.e. the vapor evaporating
from the Japan Sea in the winter season and the vapor mostly from the Pacific Ocean
in the other season (see 2.4.3). October and March are transitional months of these two
seasons. The variations parallel to the Craigs meteoric line in each seasons are due to
differences in the isotopic fractionation in cloud forming processes (see 2.4.2).

Fig. 2.6 Seasonal variation in D and
18
O of monthly collected precipitation from
1991 to 1995, at Akita.

18
O,
D, D, D, D,
D

18
O
1 7 1 7 1 7 1 7 1 7
-15
-10
-5
0
-150
-100
-50
0
91
92 93 94 95
21

Fig. 2.7 Relationship of D and
18
O of monthly collected precipitation. The
numbers show each month, of which values are averages for 5 years shown
in Fig. 2.6.

Fig. 2.8 Relationship of annual mean D and
18
O of precipitation during 19 years
(1982 ~ 1999), at Akita.

-90
-80
-70
-60
-50
-40
-30
-20
12 -11 -10 -9 -8 -7 -6 -5 -4

18
O,
1
2
3
4
5
6
7
8
9
10
11
12
D,
D = 8
18
O + 10

-60 -60 -60 -60
-55 -55 -55 -55
-50 -50 -50 -50
-45 -45 -45 -45
D=8 D=8 D=8 D=8
18 18 18 18
O+10 O+10 O+10 O+10

18 18 18 18
O, O, O, O,
D
-9.5 -9.5 -9.5 -9.5

-9 -9 -9 -9 -8.5 -8.5 -8.5 -8.5 -8 -8 -8 -8 -7.5 -7.5 -7.5 -7.5
Chapter 2
22
(d) Anual mean value
Annual mean values of isotopic ratios of precipitation for one year can be
obtained through averaging of monthly values weighted with precipitation amount of
each month. In Fig. 2.8, the annual means for 18 years from 1982 to 1999 are shown.
In such averaging, generally speaking, the seasonal variation is smoothed, and fairly
constant values are obtained. Even though, the annual mean values for 18 years show
significant variations from 47 to 59 in D and from 7.9 to 9.3 in
18
O. Also,
the d-values (deuterium excess), what stands for a constant corresponding to 10 in Eq.
(2-1), or D-8
18
O (see 2.4.3), are in a range from 12 to 18. These variations are due to
differences in contribution of individual monthly precipitations in each year.

2.4.2 Isotopic fractionation in precipitation process

The isotopic fractionation in precipitation process can be divide into three, i.e.,
evaporation of source vapor, condensation into cloud, and evaporation from falling
raindrop. At first, we examine a quite simple model of condensation in which cloud
forming (condensation ) and remove out of condensed cloud (falling of rain drops)
happen at the same time, as shown in Fig. 2.9. At the first step, 10 % of the original
vapor is condensed into liquid phase, and the liquid phase is immediately separated
from residual vapor. The residual vapor moves to the next step. Where, 10 % of the
vapor is condensed as similarly in the first step, and then the condensed liquid is
immediately separated from the residual vapor. This process is repeated step by step.
An isotopic fraction takes place during the separation of vapor and liquid. If an
equilibrium fractionation is applied to this separation, the extent of fractionation must
change with progress in the step, because this kind of successive condensation, in fact,
is caused by cooling of ascending air-mass, and also because the isotopic fractionation
factor between vapor and liquid changes with temperature. To make the model simple,
however, we assume a constant fractionation. Also, instead of a fractionation factor, a
difference of value between liquid and vapor is used.
In Fig. 2.9, the change of hydrogen isotopic ratio (D) with the progress of step is
shown, using the following fractionation extent.

= D (liquid) D (vapor) (2-4)
= 100 ()

This fractionation factor corresponds to the equilibrium one at about 8 C. And
100 is chosen for D of the source vapor, assuming vapor nearly equilibrated with
can be diVide inlo lhree, i.e.,
23
seawater. D of the residual vapor and the separated liquid are calculated by a material
balance equation as follows.

D
o
= 0.9D
v
+ 0.1D
l
(2-5)
D
l
= D
v
+

where the suffixes, o, v and l stand for the vapor coming from the former step, the
residual vapor and the condensed liquid. The results of calculation are shown in Fig.
2.9, which shows that D of the residual vapor gradually decreases while progress in
condensation, and reaches 200 at the 10th step where the residual rate of vapor is
35 %, and 300 at the 20th step where the residual rate of vapor is 12 %. Also D of
the separated liquid decreases in parallel to the vapor. In case of oxygen isotope, the
idea is entirely same, except for the extent of isotopic fractionation.

0 1
2 3 4 5 Step

-100 -110 -120 -130

-140 -150 -200 -300
10 20
-10 -20 -30 -40 -50 -100 -200
D
l

Fig. 2.9 Change in D of vapor through successive condensation as a model of cloud
formation (see text).
Chapter 2
24
The above model can be applied to a rainfall from a warm air-mass ascending
along a discontinuous plane in contact with a cold air-mass, or rainfalls of warm front
type and cold front type. In such cases, the ascending or the cooling progress from a
position near the front to away from the front. Therefore, if the isotopic ratios of
rainwater are similar to those of cloud water, or the liquid phase in the above model,
the isotopic ratios of rain water are high near the front and gradually decrease towards
away from the front. At a observation point, if a discontinuous plane type rainfall
passes through near to away from the front, decrease in isotopic ratios with time are
observed and vice versa (see 3.1).
In case of convective cloud, the successive condensation takes place vertically
from bottom to top of the cloud, and the isotopic ratios of rain drop (or snow) are
controlled by processes of cumulative condensation (snow, hailston) and capturing of
cloud droplet. The variations with time depend on falling time of raindrop and snow
from various parts of the cloud, and is quite complicated matters (see 3.1).
Although a finite difference method was used in the above model calculation, a
differential is more accurate and convenient. If an infinitesimal portion of vapor is
condensed into liquid, and if an isotopic equilibrium attains between the liquid
condensed and the residual vapor, the following differential equation of material
balance is obtained.

RdN + NdR = RdN (2-6)

where R and N are isotopic ratios (D/H or
18
O/
16
O) and amount of the vapor,
respectively and is the isotopic fractionation factor between liquid and vapor. If is
a constant, the following equation is obtained by integration of Eq. (2-6),

O O
ln 1 ln
N
N
R
R

F ln 1 (2-7)

where the suffix, o means the initial value, and F stand for the residual rate of vapor.
This equation was initially presented by Rayleigh (1902) to explain composition
change in distillation of binary mixture, and hence is called the Reyleigh distillation
equation. In Fig. 2.10, the change of D of the vapor with F is show at the same
condition as the calculation in Fig. 2.9, i.e. = 1.100 ( = 100 ), and D
o
= -100 .
Al an
slands Ior lhe residuaI rale oI Vapor.
is shon al lhe same
25
The Eq. (2-7) is approximately expressed as.

= lnF +
o
(2-8)

and for the liquid.

= lnF +
o
+ (2-9)

From two equations of Eq. (2-9) for hydrogen and oxygen isotopic ratios, the
following equation is derived.

D

H
O

18
OD
O

H
18
O
O
(2-10)

This linear equation may be basically applied to explain the Craigs meteoric
relationship. As a matter of fact, however
H
/
O
depends on temperature, for instance,
it is 8.6, 9.1 and 9.5 at 20C, 10C and 0C, respectively, and the Craigs relationship is
not simply explained by successive condensation processes mentioned above.

Fig. 2.10 Change in D of vapor through condensation controlled by a Rayleigh
distillation equation (
l-v
= 1.100).

-350
-300
-250
-200
-150
-100
1 0.5 0
F
D,

Chapter 2
26
2.4.1 Isotopic fractionation on source vapor

The source vapor of precipitation is supplied through evaporation of sea water and
also inland water, and its isotopic ratios are controlled by isotopic fractionation in
evaporation and mixing rate of two kinds of vapor from oceans and inland.
In the evaporation processes from oceans as well as from inland, if the vapor is
isotopically in equilibrium with the water, the constant term of D
O

H
/
O

18
O
O
in
Eq. (2-10) becomes zero. Therefore, the constant term of +10 in the Craigs
relationship must be due to certain non-equilibrium effect, or kinetic effect on the
isotopic fractionation in evaporation. The isotopic fractionation including such kinetic
effect is expressed as follows:

n
=
e

k
(2-11)
or
n
=
e
+
k
(2-12)

where, the suffixes n, e and k mean net, equilibrium and kinetic, respectively. If the
kinetic effect is caused by differences in diffusivity in air among three isotopomer of
water vapor (
1
H
2
16
O,
1
H
2
H
16
O, and
1
H
2
18
O), the kinetic effect is expressed as the
followings (Craig and Gordon, 1965).

k

m
m

n
2
(2-13)
or

H
k
= n 27.4 (2-14)
O
k
= n 54.1 (2-15)

where m and m are molecular weights of the heavier isotopomer (19 or 20) and the
lighter one (18), and n is a constant between 0 and 1 depending on the contribution
degree of the kinetic effect .
In a case of no kinetic effect, if it is assumed that the equilibrium effect is constant,
and
H
= 80 , and
O
= 10 , the vapor evaporating from seawater (D = 0,
18
O =
0 ) is plotted at the point A in Fig. 2.11. The D and
18
O of precipitation show a
linear correlation of which slope is ,
H
/
O
8 and their relationships is expressed
as,

,
H
/
O
27
D = 8
18
O (2-16)

or this line passes through the point O (D = 0,
18
O = 0 ). On the contrary, if a
kinetic effect is included and if n in Eqs. (2-14) and (2-15) is 0.1, the vapor from
seawater is plotted at the point B in Fig. 2.11, because of combination of the
equilibrium effect (OA) and the kinetic effect (AB). Because D and
18
O of
precipitation changes according with a linear line of slope 8, their relationship is
expressed,

D = 8
18
O + 40.5 (2-17)

In case of the Craigs line, +10 corresponds to the case of n=0.025 (the point C).
If the relationship of D and
18
O of precipitation is expressed by the following
equation,

D = 8
18
O + d (2-18)
or
d = D - 8
18
O (2-19)

the d-value (deuterium excess) shows degree of the kinetic effect, and it is quite useful
to distinguish source vapor. For instance, in Fig. 2.7, the winter precipitation has higher
d-values than the other seasons. This is due to the source vapor in the winter season
coming from the Japan Sea, which is subjected to the kinetic effect more than the
vapor coming from the Pacific Ocean in the other seasons. Moreover, the same kinetic
effect is observed during evaporation from rain droplet falling. In such case, D and
18
O of rain increase proportionally with slope smaller than 8, or 7 ~ 5.
Alternatively, if the correlation factor between D and
18
O is variable, and shifts
little from 8 in actual precipitation, the d-value must change depending on difference
between the actual factor and 8 (e.g. Dansgaard, 1964).

Chapter 2
28

Fig. 2.11 Relationship of D and
18
O showing kinetic effects for source vapor and
precipitation (see text).

2.4.2 Global features

In 1961, the International Atomic Energy Agency (IAEA), in co-operation with
the World Meteorogical Organization (WMO), started measurement of
2
H,
3
H and
18
O
concentrations of monthly collected precipitation at worldwide stations more than one
hundred. This survey has been continued until recently, though there were some
changes in stations. The survey results had been compiled in the IAEA Technical
Report Series (e.g. IAEA, 1969) at an interval of several years, while, at the present,
can be known through the IAEA internet site, i.e. the web site of the Global Network
for Isotopes in Precipitation (GNIP) and Isotope Hydrology Information System
(ISOHIS: http://www.isohis.iaea.org/)
Dansgaard (1964) examined the results of
2
H and
18
O concentrations in the first
two years, and found the following four trends, i.e. the lower the D and
18
O of
precipitation are, (a) the higher the latitude is (latitude effect), (b) the higher the altitude
is (altitude effect), (c) the more the precipitation amounts (amount effect), and (d) the
more inland the station is located (inland effect). Although these trends are apparent
one, must be able to explain on theoretical bases.
The latitude effect means almost the same feature as shown in Figs 2.2 and 2.3.
In fact, the variation in D or
18
O of annual mean precipitation with latitude is
outlined in Fig. 2.12. The difference between low and high latitudes is about 15 in
18
O (120 in D) and much smaller than the extent of variation shown in Figs 2.2 or

-20 -15 -10 -5
+50
+40.5
+10.0
O
-50
-100
A
B
C

18
O,
D,
D=8
18
O
n=0.15 0.10
0.05
29
2.3. A large variation is found only on the mountainside from the coast to the plateau
(ca. 3000 m above sea level) in the Antarctica. These worldwide variations must be
controlled by global water circulation, which is caused by atmospheric circulation,
meteoric precipitation, evaporation from the surface, and other processes. Jouzel et al.
(1987b) performed computer simulations of the worldwide isotopic variation using
NASA Goddard Institute for Space Studies (GISS) atmospheric general circulation
model (GCM), additionally taken in to account of water vapor transport, atmospheric
condensation processes, surface evaporation and groundwater hydrology. In the model,
the surface is divided into ca. 800 grid spaces and the atmosphere is vertically divided
into 9 layers, and then water transport between the divided blocks were simulated on
the basis of various meteorologic observation data. They presented fairly good
simulations of relationships of
18
O vs. annual surface temperature, D vs.
18
O, and
others.
The GCM must be useful for simulations of precipitation isotopic features. In
fact, water transport can be traced by the GCM with discerning water vapor coming
from different regions of the ocean. For example, Numaguchi (1999) devided the
ocean into 8 regions, and then water from each region was traced by the GCM. He
determined fractions of water vapor from each source region in total water vapor
bearing precipitation and concluded that recycling of water from land was considerable
for summer precipitation at inland area of the Eurasian Continent. To trace water vapor

-60
-40
-20
0
0 30 60 90
Antarctica
Latitude

18
O,

Fig. 2.12 Out line of variation in
18
O of annual mean precipitation with latitude.
laken inlo
Chapter 2
30
transport by the GCM, the tracing method with discerned water is more suitable than
the tracing method with isotopes, because isotopic composition of water in each region
of the ocean is not significantly different to each other. In the case of discerned water,
however, it is impossible to compare the calculated result to observed result. On the
other hand, isotopic composition of precipitation can be compared between calculated
and observed results. It can be said, therefore, that both methods are important for a
research on water cycle, and require more improvement. Moreover, it is really
necessary to increase observational facts which are used in the GCM.
The altitude effect means that D and
18
O of annual precipitation decrease with
increase of altitude on mountainside as seen in the Antarctica. This decreasing trend
may partly be attributed to forced ascending of air-mass on the slope, resulting cooling
of the airmass, and progressing of isotopic fractionation in successive condensation of
vapor as expressed by the Rayleigh distillation equation (Eq. 2-7). Another possible
reason is that successive condensation and separation of condensate (precipitation)
progress often from coast to inland without regard to topography. This is a kind of the
inland effect, and mostly mixed up with the real effect of slope.
The amount effect is basically due to the degree of condensation of source vapor,
i.e. the ratio of amount of total precipitation to amount of the source vapor. In fact,
however, vapor supplies continuously into the air-mass where precipitation takes place,
and at the same time it disperses out from the air-mass. The amount effect must be
explained by some dynamic process of vapor transport.
The inland effect is explained by two processes. One is effect of vapor
evaporating from surface water (fresh water) on land. When an air-mass traverses a
continent, the mixing ratio of vapor from land in the source vapor of precipitation
increases gradually toward inland, and consequently the isotopic ratios of precipitation
decrease toward inland, because the vapor from land has isotopic ratios lower than the
vapor from ocean. This trend is observed in a fairly large scale of several hundreds to
several thousands of kilometers. Another process is progress of the Rayleigh
distillation type precipitation from coast to inland. This is observed in rather small
scale of several tens to several hundreds of kilometers.

2.5 Ice caps.

Isotopic character of ice caps on the Antarctica as well as the Greenland have
been actively studied, and the lowest value in natural water (-450 in D and 55
in
18
O) were found at inland area of the Antarctica. The isotopic character of
31
Antarctic ice cap can be outlined as the isotopic ratios increase from about 150 in
D and 20 in
18
O at the coast to about 450 in D and 55 in
18
O at the
edge of the plateau at about 500 km inland, and the latter value is kept almost constant
on the plateau.
Since the beginning of isotopic study of ice cap, strong interest has been taken in
ice core study, because lower layers of ice cap must be ancient one and is expected to
have information about climate at that time. Results about several ice cores deeper than
2000 m (1 ~ 3 10
5
years before present) showed variations in D and
18
O similar to
each other. From ages of ice layers, it is explained that the variations are consistence
with the series of glacial and interglacial periods, and D and
18
O are low in glacial
periods, and high in interglacial periods. An example of such variation is shown in Fig.
4.1 in Chapter 4, about ice core at the Dome Fuji station of Japan. In order to know
ancient climate, it is necessary to estimate change in air temperature from the variation
in D and
18
O of the ice. In such case, the correlation factors between D or
18
O and
air temperature in Eqs. (2-2) and (2-3) are commonly used (e.g. Jouzel et al, 1987a).
However, Eqs. (2-2) and (2-3) show correlation in the spatial variation at the present,
and it is uncertain whether or not the correlation factors for the spatial variation at the
present is applicable for the variation in different climate periods.

2.6 Surface water and groundwater

2.6.1 River water

Although river water should originate from meteoric precipitation, relationship of
these two waters has not clearly understood. It is often said that the isotopic ratios of
river water are nearly same as the annual mean values of precipitation in the
surrounding area. At the same time, it is the fact that one third or more of precipitation
are returned into the atmosphere through evapo-transpiration processes, and it is not
obvious whether or not the isotopic ratios of water retuned into the atmosphere is the
same as those of the residual part which is discharged into river. Lots of observed
results have been reported about the isotopic ratios of river water, while precise
comparison of those results with precipitation is quite few.
In Fig. 2.13, isotopic ratios of river water are shown within rather small drainage
systems near Akita. All of these isotopic ratios are fairly constant within variation of
6 in D and 0.8 in
18
O. And also, no seasonal variation is observed (e.g. at P3),
and no significant differences are observed among three drainage systems at P2, P4,
Chapter 2
32
and P3 where the river water is mixture of discharge from the eastern (P4) and central
drainages.
In Fig. 2.13, annual means of precipitation at P1 are also shown for the period of
the river water observation (1982 ~ 1985). There is no significant difference in D
between the river water and the precipitation, while the
18
O of river water seem to be
little lower than those of precipitation. This difference may be due to two possible
reasons, one reason could be the difference in the annual mean of precipitation
between P1 and the three drainage areas, because these three drainage areas are
situated at more inland and more mountain side than P1. The other possibility is the
difference between the annual means of precipitation and the isotopic ratios of water
discharged to the rivers, because some difference in the isotopic ratios must occur
between water discharged to river and water involved in evapo-transpiring to
atmosphere.

Fig. 2.13 D and
18
O of river water in three small drainage systems located at eastern
side of Akita. P2~5 show localities where the river waters were colleted. The
collection times are shown in the style of month/year. At P1, the observation
of precipitation mentioned in the text (2.4.1) has been continued. Small dots
with numbers show altitudes above sea level.

33
2.6.2 Discharge to river

In case of discharge of precipitation to river, two manners are considerable. One is
flowing on the surface, which is called the direct runoff or the surface runoff. The other
is that the precipitation once infiltrates underground and becomes groundwater, then
the groundwater is discharged to river, which is called the base flow or the base runoff.
From continuous flowing of river water even in a period of no rainfall, the base runoff,
or the discharge of groundwater is obvious. As shown in Fig. 2.13, the base flow, in
general, has fairly constant isotopic ratios similar to the annual mean precipitation. In
some drainage systems, however, large variation is observed that follows precipitation
pattern (e.g. Frederickson and Criss, 1999). This difference is due to difference in mean
residence times of groundwater (see 2.6.4).
On the contrary, during and soon after a rainfall, especially a heavy rainfall, rising
of river water often occurs, and some part of precipitation is expected to flow out to the
river directly. In such case, the rate of direct runoff can be obtained through the
observation of change in the isotopic ratios of river water, if isotopic ratios of the
precipitation are considerably different from those of the base flow (see 6.1.1). In Fig.
2.14, one example is shown about the determination of direct runoff rate observed at
P4 in Fig. 2.13 (Matsubaya et al., 1990). In that case, it was a 85mm rainfall for 18
hours. 12 hours after the beginning of rainfall, the flow rate of river started increasing,
and at the same time
18
O of river water started decreasing. Because
18
O of the base
flow and the rainwater are 9.5 and 11.2 , respectively, the mixing ratio of these
two waters can be calculated from
18
O of the river water, as shown by the shaded part
within the flow rate graph. The mixing rate becomes about two thirds at the highest. In
excess discharge caused by this rainfall, however, the mixing rate of rainwater is only
15 %, and the rest 85 % is discharged from groundwater (same as the base flow). This
means that the major part of precipitation once infiltrate underground, and the same
amount of groundwater push out to the river. Such small rate of direct runoff is
commonly observed in other areas where the ground surface is covered by vegetation
(e.g. Germany, Canada). However, if the character of ground surface is different (e.g.
hard rocks like granite, limeston, and so on), or if the climatic condition is different (e.g.
arid area), the direct runoff rate should be different from the above case.
il as a 85 mm rainIaII Ior J8
Chapter 2
34

Time,hr
24

18
O,
Flow Rare,
` `` `10
3
m
3
/hr
precipitation,
mm/hr
48 72 0
0
100
200
300
0
10
20
30
40
50
60
70
0 72
-11
-10
-9

Fig. 2.14 Rate of direct runoff shown by shaded area in the flow rate change,
calculated from the
18
O change of river water at the Iwami River, Akita.

As mentioned above, in a small drainage system, the isotopic ratios of river water
are similar as those of groundwater. In a large drainage system, however, the isotopic
ratios of river water are the average values of groundwater discharged in the area above
the observation place, while the groundwater has isotopic ratios representative of local
and rather small area. Therefore, fairly large difference is often observed between the
river water and the groundwater in downstream areas. In Fig. 2.15, one example is
shown about Shinano river, which is the 3rd biggest river in Japan. At the upper stream
areas, the difference between the river water and the groundwater are 2 ~ 6 in D,
and 0.6 ~ 0.8 in
18
O, while those are 10 ~ 18 in D and 1.8 ~ 2.0
18
O at the
downstream area near coast. This means that the isotopic ratios of river water represent
the average character of whole drainage system above the observation point, but not
the local character at the observation point.
35

Fig. 2.15 Comparison of the differences in D and
18
O of river water (R) and
groundwater (G) between the upper and lower Shinano River

2.6.3 Lake water

The isotopic ratios of lake water are, generally, similar to those of river water
flowing into the lake. In particular case, such as no outlet river, the isotopic ratios of
lake water are modified through evaporation as well as isotopic exchange with
atmospheric moisture. In lakes, water supply by inflows as well as precipitation on the
lake is balanced with sum of outflow (including leakage from the bottom) and
evaporation. If the rate of evaporation is considerable, roughly more than a few per
cent of the outflow, the modification becomes significant, and the isotopic ratios of
lake water are generally heightened. In such cases, a rate of changes in D and
18
O,
or a slope of D vs.
18
O relationship is controlled by relative extent of the evaporation
Chapter 2
36
and the isotopic exchange.
In a case that the extent of evaporation is much larger than that of the isotopic
exchange, for example, lakes in arid regions or hot water lakes in geothermal areas, the
slope is mainly controlled by the kinetic evaporation mentioned above (2.4.3) and
expressed by a ratio of
n
(Eq 2-12) for hydrogen and oxygen isotopes,

O
k
O
e
H
k
H
e
O
n
H
n

S
(2-20)

where S stands for the slope. In the case of most lakes, the slope is in a range from 2
to 6, and can be explained by Eq. (2-20) as the following examples. At 15C, when
e
H
and

e
O
are 90 and 10.2 , respectively, if n is in Eq. (2-14) and (2-15) is 0.1 or 0.2,
S becomes 5.9 or 4.5, respectively. In a case of hot water lake, the slope becomes
gentle, because of smaller equilibrium effect. For example, at 100C (
e
H
= 28 ,
e
O
= 5.0 ), S is 2.9 or 2.1 for n=0.1 or 0.2, respectively.
In a case of humid regions, the evaporation and the isotopic exchange take place
at the same time. Craig and Gordon (1965) discussed theoretically this process in detail,
and their model has been applied to many lake studies (e. g. Sakai and Matsubaya,
1977), and also evaporation from hot water lakes (e. g. Matsubaya and Sakai, 1978).
If the Craig and Gordon model is extremely simplified, the effect of evaporation is in
proportion to (1-h), and the effect of isotopic exchange to h, where h is relative
humidity, and the isotopic ratio of lake water in a steady state, when the isotopic ratio
of vapor evaporating from the lake is equal to the isotopic ratio of inflow, is shown as,

L
= (
I
+
e
+
k
) (1-h) + (
A
+
e
)h (2-21)

where the suffixes, L, I and A stand for lake, inflow and atmospheric moisture.
From Eq. (2-21), it is obvious that the isotopic ratios of lake water in humid
regions are strongly affected by the isotopic ratios of atmospheric moisture. For
example, in Japan where the annual mean humidity is about 70 % (h=0.7), as shown in
Fig. 2.16, a line connected inflow and lake reaches a common region in D vs.
18
O
similar to the sea water, without regard to localities or isotopic ratios of inflow. This
implies that the isotopic ratios of lakes are controlled by the atmospheric moisture
coming from ocean.

iI n is in Lqs.
37

-15 -10 +5 -5
-50
-100
D,

18
O,
Steady State
1
2
3

Fig. 2.16 D vs.
18
O of lake water from some lakes in Japan, where the evaporation of
lake water is considerable as compared with flow out and leakage. 1.Ikeda-ko
area, 31 14N, 13034E (Sakai and Matsubaya, 1977). 2.Kusatsu-Shirane
area, 3636N, 13833E (Ouba et al, 2000). 3.Masyu-ko area, 4335N,
14433E. Steady State, see the text.

If outflow as well as leakage are considerable as compared with the evaporation,
the isotopic ratio of lake water is expressed as,

L
= x
L-ss
+ (1-x)
I
(2-22)

where x is the rate of evaporation and
L-ss
stands for the steady state value expressed
by Eq. (2-21).

2.6.4 Groundwater and soil water

The relationship among precipitation, soil water and groundwater may be able to
understand as shown in Fig. 2.17. Although many processes have remained
unexplained, roughly speaking, most of precipitations once infiltrate into soil. Then
one third or half of them are returned into atmosphere by evaporation and
evapotranspiration, and the rest infiltrates into saturation zone, where interstice of soil
grain is filled up with water. In case of mixing of precipitation infiltrating, two
nba .,
Chapter 2
38
processes should be considered. One is complete mixing at rather shallow part, perhaps
above 1 ~ 2m depth, and isotopic ratio of the soil water becomes homogeneous (see
6.3.3). Another is infiltration in order of precipitation, and the soil water in individual
depths keeps the original isotopic ratio of precipitation infiltrating (see 8.3.2). The
isotopic ratios of water in saturation zone may be rather similar to those of annual
mean precipitation. However, some differences are expected, because of differences
between the part returned into atmosphere and the residue, and also due to occurrence
of isotopic fractionation during the infiltration. In the evaporation of soil water and in
the evapo-transpiration through plant, little isotopic fractionation is generally expected,
because of uni-direction (irreversible) flowing of water (see 3.2.2). However, the rates
of evaporation and evapo-transpiration may vary in individual rainfall depending on
amount and intensity of the precipitation, interval between the rainfall and the fomer
one, and seasons. Therefore, as a result of difference in the isotopic ratios of individual
precipitation, certain difference must occur between annual mean precipitation and soil
water. The isotopic fractionation during infiltration is begun quite recently to examine.
In case of recharge process of groundwater, two paths should be considered.
One is recharge with soil water in saturated zone, and another is recharge with
precipitation flowing directly through some channel. Both processes may be actually
takes place, but the detail is not obvious. An idea of groundwater reservoir is generally
reasonable, and two extreme ideas, a homogenous tank model and a piston flow (plug
flow) model are considered, as shown in Fig. 2.18. If a groundwater is well mixed in a
reservoir and becomes homogeneous (the homogeneous tank model), seasonal isotopic
feature of precipitation and also time sequence of tritium content are smoothed, and the
degree of smoothing depends on the size of reservoir, or the residence time of
groundwater (Brown, 1961 ; Kusakabe et al, 1970), and the residence time of
groundwater can be obtained from the tritium content (see 8.3.2). In Fig. 2.19, an
example of difference in the residence time is shown about two springs which are
located in a distance of 800 m at Yachi, about 90 km south of Akia. One (Sp 1) shows
almost no seasonal variation in the isotopic ratios, while the other (Sp 2) shows large
seasonal variation like precipitation at Akita. This means that the mean residence time
of the spring 1 is long enough to disappear seasonal variation of precipitation, which
should be longer than several years (Kusakabe et al, 1970), while the mean residence
time of the spring 2 is short, and the precipitation is quickly discharged, perhaps 2 ~
3months after recharge. Such rapid discharge suggests some channel through which
precipitation can reach the groundwater reservoir in a shot time. In the case of piston
flow model, groundwater flows continuously keeping the order of infiltration. In this
case, the tritium content of groundwater shows the time since the infiltration, or the age
; Kusakabe et al.,
al.,
39
Precipitation
Evaporation
Evapo-transpiration
Infiltration
Soil water (saturated zone)
Groundwater (involved in discharge process)
Groundwater (isolated from discharge process)

Fig. 2.17 A basical idea about the relationship among precipitation, soil water and
groundwater.

Precipitation Groundwater
t=1
2
3
10
n
n-10
20
Precipitation
Groundwater
J
J
N
J
= T
r

Fig. 2.18 Two ideas of groundwater reservoir. Left, a piston flow type (t,year), and
right, a homogeneous tank type (J,N,Tr, recharge rate, groundwater amount,
mean residence time, respectively).
a pislon IIo l,pe |l, ,ear),and
right, a homogeneous tank type (J, N, Tr, recharge rate, groundwater amount,
Chapter 2
40
(see Chapter 5). About the stable isotopic features of such a piston flow type
groundwater, little is examined, for example, whether or not seasonal character, feature
of individual precipitation, and time variation of one precipitation are preserved.
If groundwater infiltrates into deeper part, the groundwater may be separated from
the discharge system into river, and involved in long time (perhaps 10
3
~ 10
5
years)
circulation at the lower crust. In fact, several groundwaters are often obtained from
different depths in the same area, and sometimes certain differences in the isotopic
ratios are observed among them. For example, in a mining tunnel at Odate area about
80 km north of Akita, the groundwater discharged from 300 ~ 350 m depth have
isotopic ratios of -63 ~ -67 in D and -9.9 ~ -10.6 in
18
O, which are lower than
a shallow groundwater (-54 in D, -8.9 in
18
O) and a river water (-56 in D,
-9.2 in
18
O) in the same area. The infiltration processes of such deeper
groundwater and their isotopic character are not known.

18
O,
D,
-80
-70
-60
-50
-40
-13 -12 -11 -10 -9 -8 -7
D=8
18
O+10
Sp 2
Sp 1

Fig. 2.19 Seasonal variation in D and
18
O of two spring waters at Yachi, Akita.
41
References

Anati, D.A. and Gat, J.R., Restricted marine basins and marginal sea environment. In
Handbook of environmental isotope geochemistry, Vol. 3, The marin environment,
A. ed. by P. Fritz and J. Ch. Fontes, Elsevier, pp. 29-73, 1989.
Brown, R. M., Hydrology of tritium in the Ottawa Valley. Geochim. Cosmochim. Acta,
21, 199-216, 1961.
Craig, H. Isotopic variations in meteoric waters. Science, 133, 172-1703, 1961.
Craig, H. and Gordon, L. I.., Isotopic oceanography : Deuterium and oxygen-18
variations in the ocean and the marine atmosphere. In Marine geochemistry.
Proc. of Symp. at University of Rhode Island, ed. By D.R. Schink and J. T.
Corless, pp. 277-313, 1965.
Dansgaard, W., Stable isotopes in precipitation. Tellus, 16, 436-468, 1964.
Ferronsky, V. I. and Brezgunov, V.S., Stable isotopes and ocean mixing. Handbook of
environmental isotope geochemistry, Vol. 3, The marine environment, A. ed. By P.
Fritz and J. Ch. Fontes, Elsevier, pp. 1-27, 1989.
Frerronsky, V. I. and Polyakov, V. A., Environmental isotopes in the hydrosphere. John
Wiley and Sons. pp. 466.,1982.
Frederickson, G. C. and Criss, R. E., Isotope hydrology and residence times of the
unimpounded Meramec River Basin, Missouri. Chem. Geol., 157, 303-317, 1999.
Friedman, I., Redfield, A. C., Schoen, B. and Harris, J., The variation of the deuterium
content of natural waters in the hydrological cycle. Rev. Geophys., 2, 177-224,
1964.
Fritz, P. and Fontes, J. Ch., Handbook of environmental isotope geochemistry, Vol. 1,
The terrestrial environment, A. Elsevier, pp. 545, 1980.
Fritz, P. and Fontes, J. Ch., Handbook of environmental isotope geochemistry, Vol. 2,
The terrestrial environment, B. Elsevier, pp. 557, 1986.
IAEA Environmental isotope data No. 1: World survey of isotope concetration in
precipitation (1953-1963). Technical Rep. Ser. No. 96, 1994.
Jouzel, J., Lorius, C., Petic, J.R., Genthon, C., Barkov, N.I., Kotlyakov, V.M. and
Petrov, V.M., Vostok ice core : a continuous isotope temperature record over the
last climatic cycle (160,000 years). Nature, 329,403-408, 1987.
Jouzel, J., Russell, G.L., Suozzo, R.J., Koster, R.D., White, J.W.C. and Broeker, W.S.,
Simulations of the HDO and H
2
18
O atmospheric cycles using the NASA GISS
general circulation model : The seasonal cycle for present-day conditions. Jour.
Geophys, Res., 92, 14739-14760, 1987.
I.,
J969.
a. a.
b.
Chapter 2
42
Kendall, C. and McDonnell, J.J., Isotope tracers in catchment hydrology. Elsevier, pp.
839, 1998.
Kusakabe, M., Wada, H., Matsuo, S. and Horibe, Y., Oxygen and hydrogen isotope
ratios of monthly collected waters from Nasudake volcanic area, Japan. Jour.
Geophys. Res., 75, 5941-595, 1970.
Mason, B. and Moore, C. B., Principles of geochemistry, 4th ed., Table 9.1, p. 233,
1982.
Matsubaya, O. and Sakai, H., D/H and
18
O/
16
O fractionation factors in evaporation of
water at 60 and 80C. Geochem. Jour., 12, 121-126, 1978.
Matsubaya, O., Yoshida, M. and Tanaka-Miyamoto, K., Runoff analysis by means of
multiple isotope tracers in Iwami River drainage, Akita, Japan. Mass Spectroscopy,
38, 331-339., 1990.
Nakawo. M., Water circulation over the earth : The roles of snow and ice. In Snow
and ice science in hydrology, the textbook for the 10th IHP training course. ed.
by M. Nakawo and N. Hayakawa, Chap. 1, pp.1-17(Fig. 1-8), 1998.
Numaguchi, A., Origin and recycling processes of precipitating water over Eurasina
continent: Experiments using an atmospheric general circulation model. Jour.
Geophys. Res., 104, No.D2, 1957-1972, 1999.
Ohba, T., Hirabayashi, J. and Nogami, K., D/H and
18
O/
16
O ratios of water in the crater
lake at Kusatsu-Shirane volcano, Japan. Jour. Volcanol. Geotherm. Res., 97,
329-346, 2000.
Rayleigh, Lord, On the distillation of binary mixtures. Phil. Mag. 4, (6th ser ), 521-537,
1902.
Sakai, H. and Matsubaya, O., Stable isotopic studies of Japanese geothermal system.
Geothermics, 5, 97-124, 1977.
Turekian, K. K., The Oceans, streams, and atmosphere. In Handbook of geochemistry,
Vol. 1ed. by K. H. Wedepohl, Chap. 10, pp. 296-323, 1969. (Table 10-13)
White, D. E., Magmatic, connate, and metamorphic waters. Bell. Geol. Amer., 68, 1659-1682,
1957.
\hile, .L., Maymalic, connale, and melamorphic alers. Bell. Geol.
A m e r . , , J 6 5 9 J 6 8 2 , J 9 5 7
Water circulation in regional scale
43
Chapter 3


Isotopic composition of water varies in water cycle, namely precipitation
process in the atmosphere and hydrological processes in a biosphere on a regional
scale. Water evaporates into the atmosphere directly from water body, soil surface,
or through plants. Clouds are formed in ascending air mass, and rainfall or
snowfall occurs. Rainwater percolates into the soil, and a part or all rainwater
returns to the atmosphere. Variations in isotopic composition of water in these
processes are described in this chapter. Recently, several textbooks have been
published on water isotope hydrology (Clark and Fritz, 1997; Griffiths, 1998,
Kendall and MacDonnell, 1998; Lajtha and Michener, 1994). These books are
recommended for further reading.

3.1 Precipitation process in the atmosphere

3.1.1 Cloud type and isotopic composition of precipitation

Clouds have been classified on the basis of height and appearance. Clouds
which develop from the lower level of troposphere are considered here, because
precipitation particles are formed in them. On the basis of appearance, there are
two types of clouds. One is a cloud spreading laterally to form layers. It is,
therefore, called stratiform clouds. Vertical ascending movement of these clouds is
usually gentle, and the cloud system is relatively steady. The other type of clouds
is called cumuliform clouds, which develop vertically and vertical ascending rate
is much higher than the stratiform clouds. Cumuliform clouds are also called
convective clouds. Schematic figures of the two types of clouds are shown in Fig.
3.1. Actual clouds are, however, more complicated and consist of both types of
clouds in some cases.

Chapter 3
44

Fig. 3.1 Stratiform cloud accompanied with warm front (a) and a
life of a convective cloud (b).

Isotopic composition of precipitation (rain or snow) are usually referred as
monthly and annual mean values. However, the D and
O values vary in much

shorter period (daily, hourly or minutely) and may reflect in precipitation process
in the cloud. Figure 3.2 is a variation in the
O of snowfall observed in Sapporo,

Japan. In this figure, six major convective clouds were recognized. During the
time a cloud was passing over, the
O of snow particles varied with time. Trend

of variation, however, differs from cloud to cloud.
It is well known that linear relationship between D and
O has been
observed for monthly or annual mean values of precipitation called meteoric water
line. For the data with more shorter sampling interval (5 min to 1 hour), linear
relationship between D and
O is also observed, not for all case but often (Fig.

3.3), especially for precipitation from an isolated small convective cloud.
45

Fig. 3.2 (left) Variation in
18
O of falling snow particles observed at Sapporo,
Japan, during passage of convective clouds. Six major clouds were
identified from the variation of precipitation intensity.
Fig. 3.3 (right) Relationship between D and
18
O of precipitation particles from
a small convective cloud. Data from Sugimoto et al. (1988).

3.1.2 Isotopic compositions of cloud droplets and precipitation particles in an
ascending air parcel

The type and structure of cloud system is different from cloud to cloud.
However, in all clouds, similar phenomenon takes place, namely, cloud droplets
grow in an ascending air parcel in the cloud.
As the air parcel ascends, by cooling adiabatic expansion takes place.
Temperature decreases at dry adiabatic lapse rate until the air comes to saturation.
Then, cloud droplets form result in condensation of water vapor. Temperature of
rising air parcel further decreases at wet adiabatic lapse rate. During the phase
Chapter 3
46
change of water vapor to cloud droplets (liquid), isotopic fractionation occurs.
Changes in the
O and D of water vapor and cloud droplets during the adiabatic

expansional cooling are considered (Fig. 3.4). For instance, when an air parcel
with 70 % of relative humidity at 10 C ascends from the surface air parcel
becomes saturation at 670 m where air temperature is 3.6 C. Assuming the
O
of original water vapor to be 14 at the surface, the first cloud droplets formed
at 670 m is 3.3 . At this height, only a small fraction of vapor is converted to
cloud droplets. Accordingly, if the size of cloud droplets is too small to fall down,
then, they ascend with the air parcel. As the air parcel rises, cloud droplets grow,
and the
O of water vapor decreases because heavy water isotopes tend to enter

into the liquid phase. The
O of cloud droplets decreases with height, because

the
O of water vapor decreases with height (Fig. 3.4).

As the cloud droplets are becoming large, cloud droplet is converted to
precipitation particle, and they start fall down due to their gravity. Growth process
of precipitation particle is very complicated. Once a particle starts to fall down, the
particle can grow more by collecting small particles (collision-coalescence
process). In the case of co-existence of liquid particle and solid (ice/snow), solid
particles grow rapidly by consuming liquid particle, because saturation vapor
pressure of ice is lower than that liquid water, i.e., the air saturates for ice but
under saturation for water. Falling solid particles start melting at < 0C. Snow is
observed when solid particles reached to the surface before or without melting.
Growth and falling processes differ from cloud to cloud. That is why various
trends of variation in the
O were observed for precipitation from a cloud.

The D-
O relationship of precipitation is shown in Fig. 3.5. When cloud

droplets formed from a water vapor with a specific isotopic composition, their
isotopic composition has linear D-
O relation. Precipitation particles produced

with any combination of these cloud droplets have the same linear D-
O
relationship. A linear relationship between D and
O observed for the

precipitation from a cloud denotes the cloud was formed from a water vapor with a
specific isotopic composition on the same line.
Precipitation particles, originated from a small convective cloud, often shows
linear relationship between D and
O. However, the line for D-
O of a cloud
varies from cloud to cloud. This means the isotopic composition of water vapor,
which forms cloud, varies within a short period.
47

Fig. 3.4 Variation in
O of water vapor and cloud droplets during adiabatic

expansional cooling. The D and
O values of water vapor and cloud

droplets are calculated, assuming isotopic equilibration. Fractionation
factors at temperature T (K) are assumed as follows:
lna = 15013/T
2
0.1 for hydrogen (Merlivat and Nief, 1967)
lnb = 1.13/T
2
10
3
0.4156/T 0.20667 10
-3
for oxygen
(Majoub, 1971)
Pressure change is calculated from the following thermodynamic equation
for the air;
(Cp + Cw(rw+l))dT RT(dPa/Pa) + Td(Lvrw/T) = 0,
where Cp and Cw are specific heat capacity, rw and l are mixing ratio of
water vapor and cloud droplets, Pa and Lv are pressure of dry air and
latent heat for condensation. All cloud droplets are retained in the air
parcel, which is same as closed two-phase system in Dansgaard (1964)

Chapter 3
48

Fig. 3.5 The D and
O relationship in the cloud droplet formed from a water

vapor calculated for adiabatic cooling shown in Fig. 3.4.

3.1.3 Other factors controlling the isotopic composition of precipitation

Falling liquid particles evaporate and exchange isotopes with atmospheric
water vapor below the cloud (Freedman et al., 1962). This may cause the change
in the D and
O. Furthermore, D and
O values increase due to evaporation.

As a result, D-
O relationship changes. The magnitude of isotopic change

depends on the size of precipitation particles. Large particles fall down more
rapidly than small particles. Besides, large volume of water needs longer time to
exchange water isotopes. Accordingly, isotopic change of a large particle is
insignificant, while, it is significant in case of small particle due to evaporation. In
case of snow particles, however, the relationship between D and
O does not
change because outer surface layer of ice crystal peels off without isotope
exchange with inner molecules.

49
3.1.4 Spatial and temporal variations in the isotopic compositions of
precipitation

As described in 3.1.1, stratiform clouds are rather steady state. Therefore, if
the isotopic composition of water vapor, forming from such clouds, is constant and
if the system is under steady state, D and
O of precipitation particles shows no

temporal variation, although the D and
O vary spatially. When the cloud

system moves, precipitation particles collected at a specific site shows temporal
variation, even if the system is steady state.
Convective clouds generally have a life. Figure 3.6 is an example of
convective cloud simulated for the snowfall observed in the region along the Sea
of Japan. As cloud develops, cloud droplets are formed in the air parcels
(developing stage), then they grow large enough to fall down (takes about 40min
in Fig. 3.6) when they fall down, grow more through collision-coalecence process
(mature stage). Falling particles drag down the air, consequently, ascending
movement is suppressed, and finally descending movement takes over in the
whole cloud (dissipating stage). All particles fall down with being evaporated, and
the life of the convective cloud is over. As expected easily, the isotopic
composition of precipitation particles vary with time. Thus, the isotopic
composition of precipitation showed spatial variation if the cloud moves
horizontally.
Inland effect is well known phenomenon that decreases both
O and D of
precipitation toward inland. As described above, spatial variation in the isotopic
composition of precipitation can take place for both cloud systems like stratiform
cloud and convective cloud. The cause of inland effect differs from case to case.
Accordingly, it is easy to understand that the rate of decrease in values observed
by inland effect varies from case to case.
Chapter 3
50

Fig. 3.6 Time-height cross section of vertical velocity of air W (a), mixing ratio of
soil Qs (b),
O values of solid particles
Os (c), vertical profiles of
O of vapor
Ov (d) and solid cloud. The
O values are calculated,

assuming -14 for the
O of initial water vapor. Figures are

reproduced from Sugimoto and Higuchi (1989) with permission.

3.2 Water cycle in an ecosystem

3.2.1 Fate of rainwater enter into an ecosystem

Rainfall into an ecosystem returns to the atmosphere through various
pathways (Fig. 3.7a) with various time scale. A part of rainfall is trapped by plant
canopy, mainly on their leaves, and is due for evaporation during and after rainfall.
51
It is called interception. The amount of rainfall intercepted by the plants depends
on the vegetation type. Water vapor returned to the atmosphere at the beginning of
evaporation has lower d values than rainwater trapped on the leaf. However,
values of water on the leaf increas due to evaporation. Finally, all water trapped on
the leaf returns the atmosphere, consequently, integrated d values of water vapor
returned into the atmosphere is the same as that of water trapped on the leaf.
Rainwater reached on the surface percolates into the soil. A part of water is
taken up by plants, which is returned into the atmosphere through plants. Called
transpiration. It has been believed that water is taken up by plants with no
fractionation. Water absorbed by plant roots rises in xylen. Water returns the
atmosphere through stomata in plant leaves. When water returns the atmosphere,
lighter isotope (H
2
16
O) evaporates faster than heavier isotopes (HDO, H
2
18
O).
Consequently, leaf water enriches in heavier isotopes. Under the steady state,
however, the D and
18
O values of water absorbed by plant roots are the same as
those of water returns the atmosphere, despite the D and
18
O of leaf water are
higher than those of absorbed water due to evaporation (Fig. 3.7b).
Soil water, which is not utilized by plant, percolates into the soil, and leaves
the ecosystem. It is called run off. During the percolation, no significant isotope
fractionation occurs. However, in a shallow soil layer (usually less than 30 cm),
the D and
18
O values becomes high due to evaporation. Generally, run off takes
place through aquifer, and the water in the aquifer is called ground water.

3.2.2 Water uptake by plants

As described above, transpiration is one of the important processes in the
water cycle in the ecosystem. The d values of xylem water are the same as those of
water absorbed by plants (Fig. 3.7b). Therefore, depth of soil water absorbed by
plants can be estimated by comparing d values of water in plants with those in soil
water. For the isotopic analyses, water is extracted from plants and soils. Three
methods for water extraction are applied generally. One is a distillation in vacuum,
which is applied for both extraction from plants and soils. Water is trapped
cryogenically at liquid nitrogen temperature. Another method is water extraction
by centrifuge. This method is applied for water extraction from soil samples. The
last one is to extract water by azeotropic distillation (Revesz and Woods, 1990),
which is applied for both plant and soil. In this method, water in sample plant or
soil is distilled with tolouene at 84.1C. Figure 3.8 is an example of vertical profile
of
18
O of soil water observed in Yakutsk. Water extracted from plant is also
8
8
pIanls |Iiy. 3.7b).
Chapter 3
52
shown in the figure.
The
18
O of soil water decreases with depth. The
18
O of surface soil water
becomes high by percolation of summer rainfall and evaporation. Plant water
extracted from a larch tree at the same time was 14 , which indicates that plant
utilized water at the depth of around 20 cm originating from summer rainfall.
There are many studies on water use by plants using oxygen and hydrogen
isotope ratios of plant water. If isotopic compositions of source water showed
significant difference among source water, it is possible to estimate source water
for plants using D and/or
18
O of plant water (Ehleringer and Dawson, 1992;
Mensforth et al., 1994; Walker and Brunel, 1990). The mean depth of water
uptake is also estimated from the isotopic compositions of plant water and soil
water, if the D and
18
O of soil water shows clear vertical gradient (Dawson,
1996; Dawson and Pate, 1996; Roux et al., 1995).
Depth of water uptake by plants depends on both rooting depth of the plant
and water availability in the soil. Rooting depth differs from species to species,
and sometimes vary with moisture condition. Generally, plants growing in an arid
region have deeper roots than those in moist region, although most of fine roots
generally distribute in the shallow layer for nutrient uptake.
Water availability for plants can be measured as water potential in the soil.
When the soil becomes dry, suction (power for taking up water) increases, in soil
water potential decreases. When soil is wet enough for plant to take up water,
depth of water uptake by the plant agrees with rooting depth. As the surface soil
becomes dry, depth of soil water available for the plant becomes deep,
consequently the plant use deeper soil water than it does under wet condition.
When the isotopic compositions of soil water differs vertically, the change in the
depth of soil water utilized by plants can be seen in the isotopic compositions of
plant water.
In a conclusion, water isotopic compositions can be used for the investigation
of water movement in an ecosystem.
, 1995).
53

Fig. 3.7a (left) Fate of rainwater in an ecosystem
Fig. 3.7b (right) Change in the isotopic composition of water during transpiration.
When a plant takes up water with the isotopic composition, no
significant fractionation occurs. Under a steady state, d value of
water leaving from the plant is same as that of water taken up,
although the leaf water is enriched due to evaporation.

Fig. 3.8 Vertical profiles of
18
O of soil water observed in a larch tree at
Spasskaya Paid. Water was extracted with vacuum distillation.
Chapter 3
54
References

Clark, I. and Fritz, P., Environmental Isotopes in Hydrogeology, 328 pp, 1997.
Dansgaard, W., Stable isotopes in precipitation. Tellus, 16: 436-468, 1964.
Dawson, T.E., Determining water use by trees and forests from isotopic, energy
balance and transpiration analyses: The roles of tree size and hydraulic lift.
Tree Physiology, 16: 263-272, 1996.
Dawson, T.E. and Pate, J.S., Seasonal water uptake and movement in root systems
of Australian phraeatophytic plants of dimorphic root morphology: A stable
isotope investigation. Oecologia, 107: 13-20, 1996.
Ehleringer, J.R. and Dawson, T.E., Water uptake by plants:perspectives from
stable isotope composition. Plant, Cell, and Environment, 15: 1073-1082,
1992.
Freedman, I., Machta, L. and Soller, R., Water-vapor exchange between a water
droplet and its environment. J. Geophys. Res., 67: 2761-2766, 1962.
Griffiths, H. (Editor), Stable isotopes integration of biological, ecological and
geochemical processes. Environmental plant biology. Bios Scientific
Publishers Limited, 438 pp, 1998.
Kendall, C. and MacDonnell, J.J. (Editors), Isotope tracers in catchment
hydrology. Elsevier, Amsterdam, 839 pp, 1998.
Lajtha, K. and Michener, R.H. (Editors), Stable isotopes in Ecology and
environmental sciences. Methods in ecology. Blackwell, London, 316 pp,
1944.
Mensforth, L.J., Thorburn, P.J., Tyerman, S.D. and Walker, G.R., Sources of
water used by riparian Eucalyptus camaldulensis overlying highly saline
groundwater. Oecologia, 100: 21-28, 1994.
Revesz, K. and Woods, P.H., A method to extract soil water for stable isotope
analysis. Jounal of Hydrology, 115: 397-406, 1990.
Roux, X.L., Spatial partitioning of the soil water resource between grass and shrub
components in a West African humid svanna. Oecologia, 104: 147-155, 1995.
Sugimoto, A., Higuchi, K. and Kusakabe, M., Relationship between D and
O
values of falling snow particles from a separate cloud. Tellus, 40B: 205-213,
1988.
Sugimoto, A. and Higuchi, K., Oxygen isotopic variation of falling snow particles
with time during the lifetime of a conveitive cloud: observation and modelling.
Tellus, 41B: 511-523, 1989.
Walker, C.D. and Brunel, J.P., Examining evapotranspiration in a semi-arid region
J994.
55
using stable isotopes of hydrogen and oxygen. Journal of Hydrology, 118:
55-76,1990.
Isotopes in Snow and Ice
55
Chapter 4


4.1 Introduction

Isotopic ratio in water changes in association with varieties of phase changes
of water due to isotopic fractionation during phase change. The ratio found in
snow and ice is, thus, the results of their previous history of the phase changes.
Snowflakes are formed high in the sky as a result of the condensation of
water vapor: vapor to solid. After snowflakes are deposited on the ground, they
tend to be round in shape by exchanging water vapor between neighboring
snowflakes, while sublimation (evaporation) and condensation take place
simultaneously in a complex manner. This process is enhanced in presence of
strong temperature gradient, because vapor pressure strongly depends on
temperature. When the air temperature becomes high enough, the deposited snow
starts melting (solid to liquid), and the snow pack becomes wet. In a wet snow
pack, snow particles become round further, and the average particle size increases
significantly to be granular snow. In this process, melting of snow particles and
freezing of liquid water abundant in between snow particles take place
simultaneously. Isotopic ratio of snow and ice of precipitating snow origin, at a
certain time, is considered to be resulted by changes occurred from the ratio of
original snowflakes.
As we have seen in Chapter 2, the isotopic ratio of meteoric water is linearly
correlated with the temperature. The ratio of snowflakes formed in the sky is
considered, in general, to represent the temperature at the time of snowflakes
formation.
There are many glaciers distributed in polar and high mountain regions
including two big ice sheets each in Antarctica and in Greenland. Since glaciers
are considered as sedimentary rocks with accumulation strata (intermittent and/or
successive deposition of falling snowflakes for many years), that stores
information of the past climate/environment within them. Temporal change of past
temperature, therefore, can be reconstructed with relatively high resolution of
Isotopes in snow and ice
s I
57
Chapter 4
56
isotopic ratios in the ice core samples retrieved from glaciers. This type of study
was initiated at Greenland Ice Sheet followed by investigations in Antarctica, and
several expressions for correlating isotopic ratio and temperature have been
proposed (e.g. Robin, 1983).
Figure 4.1 shows the vertical profile of oxygen isotopic ratio of Dome Fuji
deep ice core of 2000 m long, retrieved in 1995 and 1996, East Antarctica, which
is found to cover the time period of about 300 thousand years in the past
(Watanabe et al., 1999). One can see that the temperature has varied periodically
in a range of 6 C indicating three glacial and interglacial cycles in Antarctica.

Fig. 4.1
18
O profile of Dome Fuji deep ice core.
Accumulation rate (
) and temperature difference

(T) were calculated by using present relationship
between
18
O and mean annual air temperature,
respectively. Numbers shown in the figure are
Marine Isotope Stages. Working time scale is
shown at the right. (after Watanabe et al., 1999)

58
57
Deposited snowflakes over the Antarctic Ice Sheet seems to be subjected to
varieties of phase changes, while they turn into glacier ice, through the snow
metamorphism and firnification, as a result the isotopic ratio might have changed
from its original value. In addition, diffusion of heavy molecules within ice matrix
could also have modified the depth profile of isotopic content throughout the core.
Later on, ice cores have been retrieved not only from polar ice sheets but also
from the other glaciers at low- and mid-latitude areas (e.g. Thompson et al., 1985;
1988). It has become possible to compare multiple core data from various sites to
examine both the local characteristics and global features. The post-depositional
change in isotopic ratio may be significant and needs to be assessed since glacier
ice is frequently subjected to thaw/freeze cycles at many sites in low- to
mid-latitude areas, moreover, the presence of liquid water accelerates the change
of isotopic ratio
In this chapter, the change in isotopic ratio is described, within snow and ice
after snow deposition, in association with phase changes of water substance.

4.2 Fractionation in snow metamorphism

4.2.1 Snow metamorphism

Figure 4.2 shows a series of thin section photographs of a snow layer
(Kobayashi, 1998), where Fig. 4.2a is the picture of new snow just after the
deposition. In the figure, one can identify relict structures of original snowflakes
formed high in the sky. The structure deteriorates with time to have round particles
of about 0.1 to 0.5 mm in diameter as shown in Fig. 4.2b even at temperatures
below the melting point. The change proceeds further in the snow layer to have
more round and larger particles of about 0.5 to 1 mm in diameter as shown in Fig.
4.2c. The dry snow metamorphism, taking place at sub-zero temperature, is mainly
caused by the vapor transport from ice surfaces with relatively large curvature to
those with small curvature.
The vapor pressure p in equilibrium of a curved ice surface with the radius of
r is expressed by

0
ln
p
p
=
kTr
vs
3

(4.1)
59
Chapter 4
58
where p
0
is the vapor pressure for planner ice surface,
vs
is the surface energy at
the vapor-solid interface, is the distance between neighboring water molecules
in ice matrix, k is Boltzman constant, and T is temperature. The vapor pressure,
thus, increases with the decrease in the radius of curvature. In other words, the
pressure is larger at the surface of small particles than that of large particles, and
hence water vapor flows from the former site, compensated by the sublimation
(evaporation) of the particles, to the latter site where condensation takes place (Fig.
4.3a). As a result, relatively small particles become smaller and smaller, and
disappear eventually, while large particles grows larger. The average particle size,
therefore, appears to increase with time as we have seen in Fig. 4.2.
The characteristics of the snow metamorphism are similar in wet snow, but
the rate is much faster. Suppose snow particles surrounded by liquid water as
shown in Fig. 4.3b.

Fig. 4.2 Thin sections of snow crystals. a: new snow keeping the relict
structure of snowflakes. b: individual snowflakes become round to
be compacted snow. c: individual snow particles grow and the
average size increases with time. (after Kobayashi, 1998)

60
59
The equilibrium temperature (T) at the water-solid interface, depends upon
the radius of the curvature of the interface as follows.

|
|
.
|
\
|
0
ln
T
T
=
r L
ls
o 2
(4.2)

where
0
T is the equilibrium temperature for planner ice, namely 273.15 K (=
0),
ls
o is the surface energy for liquid-solid interface, and L is latent heat of
fusion. The equilibrium temperature is relatively lower at the surface of small
particles than larger particles. There is a heat flow from large particles to small
particles, resulting in melting of the latter. The average particle size increases with
time, which is similar to the change in dry snow metamorphism.
One of the biggest differences between dry and wet metamorphisms is that
the rating process is the vapor diffusion in the former metamorphism, while heat
flow is mostly responsible in the latter process, as shown in Fig. 4.3. A simple
calculation based on equations (4.1) and (4.2) gives that the increasing rate of the
average particle size is slower in dry snow than in wet snow by about 3 to 4 orders
of magnitude. Experimental data also confirm the same (e.g. Gow (1969);
Raymond and Tusima (1979)).

Fig. 4.3 Grain coarsening in dry snow (a) and wet snow (b);
vapor diffusion and heat transport are responsible for
the rate of change respectively.
heat
water
b.Wet snow
water vapor
air
a. Dry snow
based on Lqs. |4.J) and |4.2) yiVes lhal lhe increasiny rale oI lhe
61
Chapter 4
60

Fig. 4.4 A thin section of depth hoar crystals. Water vapor
moves upward and condense at the bottom of each
bell shape crystal.

It is well known that the rate of evaporation and condensation, in dry snow
metamorphism, is enhanced in presence of strong temperature gradient in a snow
layer, that leads to a formation of depth hoar crystals in snow at the colder site
(Akitaya, 1974). This is because vapor pressure is strongly dependent on
temperature, and water vapor flows from warmer sites, where vapor pressure is
high, to colder sites, where the pressure is relatively low, and condense at the latter
sites. A thin section photograph of typical depth hoar crystals is shown in Fig. 4.4
(Kobayashi, 1998). The bell shape crystals indicate that temperature becomes low
in the top of the figure, because the condensation of vapor appears to have taken
place at the bell bottom i.e., vapor flows upward.

4.2.2 Isotopic change during grain coarsening

In order to estimate quantitatively the change in isotopic ratio of snow, in
association with the snow metamorphism, we have to know the mass of water
(either vapor or liquid) condensed or frozen onto ice particles, since isotopic
fractionation takes place in accordance with the phase change.
Wakahama (1968) examined experimentally the temporal change in particle
size distribution of snow soaked in liquid water. He found that the average particle
size increases with time, and at the same time, the size range also increases as
shown schematically in Fig. 4.5. Raymond and Tusima (1979) made the statistical
analysis on the experimental results. They found that the cumulative frequency
curve of the size distribution plotted on logarithmic scale does not change with
time, although the average size and the median size increase with time as shown in
Fig. 4.6.

62
61

Fig. 4.5 Particle size distribution of snow crystals and the
time evolution (: frequency as a function of size
v and time t). Both the average size and the range of
the distribution increase with time from t
0
, t
1
, t
2
,
and so on.

Fig. 4.6 Cumulative frequency curve for particle size
distribution of snow crystals and their temporal
change (: cumulative frequency as a function of
size v and time t). The shape of the curves, when
plotted with logarithmic scale of diameter (=v
1/3
)
are the same for any time t, but the median size
increases with time from t
1
, t
2
, t
3
and so on.

0
0.5
1
log(v
1/3
)
(
v
,

t
)
t
0
t
1
t
2
t
3
t
4
v
1/3
(
v
,

t
)
t
0
t
1
t
2
t
3
t
4
6
Chapter 4
62
By normalizing the volume v of a grain with median diameter
m
v , the following
equation is obtained by expressing the particle size distribution irrespective of
time.

a
m m
bv
av
v
v
1
) 1 ( ) ( (4.3)

where is cumulative frequency of particle size, and a and b are constants.
Equation (4.3) is shown in Fig. 4.7, for a=0.23 and b=1.55, which were obtained
experimentally (Raymond and Tusima, 1979).

Fig. 4.7 Normalized cumulative frequency curve for particle
size distribution of snow crystals: equation (4.3)
with the values of 0.23 and 1.55 for a and b
respectively.

Median volume
m
v is expressed as a linear function of time t:

m
v =
0
v + v t (4.4)

where
0
v represents the initial median volume. Based on the equations, Raymond
and Tusima (1979) derived the freezing rate S ( v , t), for a particle with the volume
v as follows.
0
0.5
1
0 0.5 1 1.5 2 2.5 3
v /v
m
(
v
/
v
m
)
size dislribulion oI sno cr,slaIs. Ly. |4.3)
64
63

S ( v , t) = ( )
)
`
+ b
v
v
a
dt
dv
m
m
1 (4.5)
This indicates that larger grains grow further than the median size while small
grains become smaller, as we have seen qualitatively in 4.2.1. At the same time,
median size, which is the critical size for either shrink or grow, increases with time.
Figure 4.8 shows schematically the change of particle size distribution with time.
Following to the above result, Nakamura et al. (2000) found that equation
(4.3) is applicable also to the surface snow layer in Antarctica, where snow is
completely dry, with the value of 0.135 for a and the same b value: (1.55). It is
considered, therefore, that equation (4.5) can be utilized also for estimating the
amount of condensed water vapor onto a particle with the volume of v .

Fig. 4.8 Schematic figure shows time evolution of particle
size distribution of snow crystals. Particles with
smaller diameter than the median size v
m
(t) become
smaller and smaller, and those with larger size grow
bigger. The median size, at the same time, increases
with time.
t
0
t
1
t
2
t
3
v t
m
( )
0
v t
m
( )
IoIIoiny lo lhe aboVe resuIl, âkamura et all. |2000) Iound lhal Ly.
considered, lhereIore, lhal Ly. |4.5) can be uliIizsd aIso Ior eslmaliny lhe
65
Chapter 4
64
Nakawo et al. (1993) experimentally examined the temporal change in
isotopic ratio of water-saturated snow. When snow particles and liquid water is
mixed and left in an isotherm condition, the isotopic ratio of both solid and liquid
phase changes with time, because both phase changes (liquid to solid and solid to
liquid) take place simultaneously as we have seen above. The total amount of
freezing onto large particles should be the same as the amount of melting on small
particles, because the system is under isotherm condition. The o values for the
total ice portion,
iz
o , therefore, is given by

df f
f
i i iz
)
+ =
0
0
) 1 ( o o o (4.6)

where
0 i
o is the initial o value for original snow particles when mixed, f is
the total fraction of freezing, and
i
o is the o value for freezing ice. Because of
the fractionation of heavy isotopes during freezing,

+ = + 1 ) 1 (
w
o o
i
o (4.7)

From equations (4.6) and (4.7), a linear relation between D o and O
18
o is
obtained, and the slope K is approximated by

( ) ( ) | |
( ) ( ) | | 1 1
1 1
0
18 18
0
18
+ +
+ +
~
w
O
iz
w D iz
O O
D D
K
o o o
o o o
(4.8)

where
D
o and
O
18
o are the fractionation factors during freezing for deuterium
and oxygen respectively, and suffix w0 indicates the value for original water when
mixed with snow particles. The estimation given by equation (4.8) is in agreement
with experimental data (Nakawo et al., 1993). The temporal change of o values
for ice and water was also estimated with equation (4.5). The calculation, however,
was not in agreement with experimental result, indicating that the diffusion of
heavy isotopes in the vicinity of large particle surfaces could be significant
(Nakawo et al., 1993). The similar analysis can be made for dry snow
metamorphism, as well, but only qualitative analyses have been made so far.
In the presence of temperature gradient, several analyses were performed. For
Irom Lqs. |4.6) and |4.7), a Iinear reIalion beleen
mixed ilh sno parlicIes. Jhe eslimalion yiVen b, Lq.|4.8) is in ayreemenl
Ior ice and aler as aIso eslimaled ilh Lq. |4.5).Jhe caIcuIalion, hoeVer,
66
, p , g

Fig. 4.9 Vertical profile of isotopic ratio of a snow block
subjected to a temperature gradient, which was
originally uniform in isotopic ratio. (after
Hachikubo et al., 2000).

A AA A111 1
0
5
10
15
-15 -14 -13 -12 -11 -10

8
O ( )
S
p
e
c
i
m
e
n

h
e
i
g
h
t

(
1
0

-
2

m
)
-120 -112 -104 -96 -88 -80
/( )
upper part
-15.7
lower part
-2.9

8
O
D
g
r
a
v
i
t
y
example, Satow and Watanabe (1985) showed that the isotopic change in dry snow
metamorphism is significantly affected in presence of horizontal ice layers that
hinder the movement of water vapor along the temperature gradient. Sommerfeld
et al. (1987) tried to estimate the effective diffusion constant of water vapor within
snow pack by an isotope analysis. Satake and Kawada (1997) examined the
vertical profile of isotopic ratio in the surface snow layer in Antarctica, and they
found that after deposition, d-parameter changes with time, owing to fractionation
in association with depth hoar formation. Hachikubo et al. (2000) examined the
change in isotopic ratio experimentally by applying a temperature gradient to a
snow block of uniform isotopic ratio. An example of the final profile of isotopic
ratio, in their experiment, is shown in Fig. 4.9.
It shows that increase in ratio at the warmer site, and vice versa, indicating that
fractionation could take place not only during condensation but also in evaporation.
Since the self-diffusion constant of water molecule in ice matrix is in the order of
10
-14
m
2
s
-1
(Hobbs, 1974), i.e. very small, however, we may have to take into
account the presence of quasi-liquid layer over the surface of the ice particles. This
was also pointed out by Johnsen et al. (2000), who examined the diffusion of
stable isotopes in polar firn and ice for a rather long time period.
65
67
Chapter 4
66
The metamorphism is much quicker in wet snow, and hence the temporal
change in isotopic ratio is discernible in a relatively short time, say in a season.
Arnason et al. (1973) and Krouse et al. (1977), for example, examined the isotopic
change in seasonal snow pack. They found that vertical profile of isotopic ratio
throughout a snow pack does not change with time significantly when snow
temperature is below the melting point, but it tends to be uniform when the snow
pack becomes wet.
Suzuki (1993) reported that the isotopic ratio increases with time for both the
total snow pack and the discharged water out of the snow pack. This can be
explained in terms of the depletion of heavy isotopes in the liquid, because heavy
isotopes tend to be in solid than in liquid. Figure 4.10 demonstrates an
observational fact that isotopic ratio is larger for snow particles than liquid water,
abundant in between the snow particles, caused by fractionation between solid and
liquid. It should be noted that isotopic ratio is almost same for solid and for liquid
near the surface, but the difference appears to increase with depth.

Fig. 4.10 Vertical profile of the isotopic ratio for solid snow
crystals (solid line) and for liquid water (broken
line) in a snow pack. The isotopic ratio is larger in
solid and smaller in liquid, and the difference
appears to increase with depth. Observed on 6th
April 1998 at Moshiri in Hokkaido, Japan.
H
e
i
g
h
t
,

c
m

0

5
0

1
0
0

68
67
Examining the temporal change for a given snow layer, Nakawo et al. (2000)
showed that the slope in D and
18
O relationship appears to decrease with depth.
These findings would be explained in terms of the acceleration of the depletion of
water as melt water percolates downward. The quantitative analysis, however, has
not been made so far.

4.3. Isotope data in ice cores

Figure 4.11 shows schematically the change from deposited snowflakes at the
surface to glacier ice through firnification. As we have seen in the previous section,
snowflakes become round and the grains grow with time. This occurs in
association with mechanical packing of snow layers owing to the overburden
pressure caused by the weight above respective layers. When the density reaches

Fig. 4.11 Schematic diagram representing the densification of
snow to firn, and ice in glaciers. The numerical figures,
in particular for depth and age are corresponding with
typical values in Greenland Ice Sheet.
69
Chapter 4
68
about 550 kg m
-3
, mechanical deformation of individual crystals starts to
accommodate further stress, and pore spaces between crystals become isolated at
the density of about 800 kg m
-3
. Since snow is permeable by definition, deeper
portion below this depth is considered to be ice, which is not permeable. The
diffusion process of heavy isotopes is considered to be different for snow and ice
because of the difference in permeability.
Dansgaard et al. (1973) showed a typical vertical profile of isotopic ratio
throughout an ice core retrieved from Greenland Ice Sheet. Figure 4.12 is a
schematic representation of their data. The isotope data show a cyclic variation
corresponding with the annual cycle of temperature: i.e., larger in summer and
smaller in winter, since isotopic ratio is linearly correlated with temperature as
mentioned in 4.1. By counting the annual cycles indicated by the cyclic variation
in isotopic data, the dating of ice cores are relatively easy and precise. This is one
of the advantages of ice cores among various proxies used for reconstructing past
climate.

Fig. 4.12 Typical isotope data found in a Greenland ice core.
S and W in the figure indicate summer and winter
layers respectively. The amplitude and the period of
the cycle decrease with depth. (Based on data of
Dansgaard et al. (1973))
70
69
It can be noticed in the figure that the period of the cycle decrease with depth,
which is attributed to the thinning of annual layer thickness as going downward,
and it is solely due to the deformation of ice. Also, the decreasing trend of the
amplitude of the cycle can be seen in association with the smoothing or
disappearance of small perturbations within a year. This is the effect of the
diffusion of heavy isotopes for a certain time period.
Suppose that there is a peak in isotopic ratio in an ice core at t=t
0
as shown in
Fig. 4.13. Because of the gradient of isotopic ratio, heavy isotopes, which are rich
at the peak depth, would diffuse toward the vicinity where heavy isotopes are
relatively poor. The rate of the diffusion depends upon the diffusion constant and
the gradient of the ratio. It is considered, for permeable snow and firn, that vapor
transport through the vacancies between snow particles, and the fractionation in
association with their condensation/evaporation are the major process for the
diffusion of the heavy isotopes. For ice portion, on the other hand, diffusion of
heavy isotopes through ice matrix or grain boundaries is considered most
responsible for the diffusion. Johnsen et al. (2000) examined quantitatively the
diffusion processes, and suggested the contribution of water films on grain
boundaries or veins are important for diffusion.

Fig. 4.13 Diffusion of heavy isotopes in a glacier. The peak
at t=t
0
decrease its height, increasing its range,
and the profile of isotopic ratio changes with time.
The change is caused by the diffusion of heavy
isotopes.
71
Chapter 4
70
In addition to the evolution of isotopic ratio from the surface to the bottom of
glaciers, significant change could occur at the bottom interface when regelation ice
is formed at the glacier bed. The isotopic fractionation in the process of
melting-freezing was studied by Jouzel and Souchez (1982) and explained in terms
of Reyleigh distillation process, although the slope in D and
18
O diagram is
different from that in precipitation process (Souchez and Jouzel, 1984).

4.4 Concluding remarks

The isotope process in snow and ice has been outlined in this chapter, in
particular the basic fractionation processes taking place within snow and ice in
association with phase changes. The importance of isotope data in snow and ice
has been highlighted with ice core analysis for reconstructing past temperature. As
we have seen, various fractionation processes, after snow deposition, significantly
affect stable isotope data in ice cores. It is extremely important, therefore, to
examine what is happening within snow and ice during the evolution of the values
in isotopic ratio, to prevent wrong interpretation.
Isotope data in snow and ice can be used for reconstructing not only past
temperature, but also past changes in water circulation. Johnsen et al. (1989)
examined isotope data of an ice core from Greenland Ice Sheet, and estimated that
the source area of the precipitation in Greenland has been subtropical ocean
throughout Glacial and Interglacial periods. Jouzel et al. (1982), and Vimeux et al.
(1999) mentioned that isotope data in ice core from Vostok, Antarctica provided
information about past temperature and/or humidity of ocean surface. These
analyses are based on d-parameter: examination of fractionation processes, for a
given ice sample, along the pathway of water vapor after the evaporation from
ocean surface, to condensation of the vapor to form snowflakes. This is because
isotope data in snow and ice represent the previous history of the phase changes of
the snow and ice in question, as mentioned in the beginning of this chapter.
Numaguchi (1999) ran a Global Circulation Model coupled with various
isotope processes, and discussed the source area of the precipitation water, and the
age of water molecules after the evaporation from ocean surface. It is considered,
therefore, isotope data in snow and ice is promising, in particular, for
reconstructing past changes in water circulation. There are many questions,
however, left unanswered. For instance, d-parameter increases significantly as
going inland of Antarctica (Petit et al., 1982; Qin et al., 1994), and Jouzel and
ûmayuchi |J999) ran a CeneraI CircuIalion ModeI coupIed ilh Various
72
71
Merlivat (1984) tried to explain the increase in terms of vapor diffusion in
super-saturation at low temperature. The present knowledge, however, is still not
enough to discuss the water circulation system, say in glacial period. For better
understanding, therefore, a lot more work is necessary on fractionation processes
with varieties of phase changes taking place in nature including those in snow and
ice.

References

Akitaya, E., Studies on depth hoar. IAHS Publication, 114, 42-48, 1974.
Arnason, B., Th. Buason, J. Martinec, and P. Theodorsson, Movement of water
through a snowpack traced by deuterium and tritium. IAHS Publication, 106,
299-312, 1973.
Dansgaard, W., S. J. Johnsen, H. B. Clausen and N. Gundestrup, Stable isotope
glaciology, Medd. Glnl., 197(2), 1973.
Gow, A. J., On the rate of grains and crystals in south polar firn. J. Glaciol., 8,
241-252, 1969.
Hachikubo, A., S. Hashimoto, M. Nakawo. and K. Nishimura, Isotopic mass
fractionation of snow due to depth hoar formation, Polar Meteorol. Glaciol.,
14, 1-7, 2000.
Hobbs, P. V. (1974). Ice Physics. Oxford, Clarendon Press.
Johnsen, S. J., W. Dansgaard, and J. W. C. White, The origin of Arctic
precipitation under present and glacial conditions. Tellus, 41B, 452-468, 1989.
Johnsen, S. J., H. B. Clausen, K. M. Cuffey, G. Hoffmann, J. Schwander, and T.
Creyts, Diffusion of stable isotopes in polar firn and ice: the isotope effect in
firn diffusion. InPhysics of ice core record. ed. by T. Hondoh, Hokkaido
University Press, 121-140, 2000.
Jouzel, J. and L. Merlivat, Deuterium and oxygen 18 in precipitation: modeling of
the isotope effects during snow formation. J. Geophys. Res., 89, 11749-11757,
1984.
Jouzel, J., L. Merlivat and C. Lorius, Deuterium excess in an East Antarctic ice
core suggests higher relative humidity at the oceanic surface during the last
glacial maximum. Nature, 299, 688-691, 1982.
Jouzel, J. and R. A. Souchez, Melting-refreezing at the glacier sole and the
isotopic composition of the ice. J. Glaciol., 28, 35-42, 1982.
7
Chapter 4
72
Kobayashi, S., Metamorphism of deposited snow. InSnow and ice science in
hydrology, the textbook for the 10th IHP training course. ed. by M. Nakawo
and N. Hayakawa, Chap. 7, 89-105, 1998.
Krouse, H. R., H. Hislop, H. M. Brown, K. West, and J. L. Smith, Climatic and
spatial dependence of the retention of D/H and
18
O/
16
O abundance in snow
and ice of North America. IAHS Publication, 118, 242-247, 1977.
Nakamura, K., M. Nakawo, Y. Ageta, K. Goto-Azuma and K. Kamiyama, Post
depositional loss of nitrate in surface snow layers of the Antarctic Ice Sheet.
Bull. Glaciol. Res., 17, 11-16, 2000.
Nakawo, M., S. Chiba, H. Satake, and S. Kinouchi, Isotopic fractionation during
grain coarsening of wet snow. Ann. Glaciol., 18, 129-134, 1993.
Nakawo, M., S. Hashimoto, Y. Ageta and N. Miyazaki, Isotope studies of a snow
layer in a temperate region isotope balance and temporal change. InPhysics
of ice core record. ed. by T. Hondoh, Hokkaido University Press, 141-151,
2000.
Numaguchi, A., Origin and recycling processes of precipitating water over the
Eurasian continent: Experiments using an atmospheric general circulation
model. J. Geophys. Res., 104, 1957-1972, 1999.
Petit, J. R., J. Jouzel, M. Pourchet, and L. Merlivat, A detailed study of snow
accumulation and stable isotope content in Dome C (Antarctica). J. Geophys.
Res., 87, 4301-4308, 1982.
Qin, D., J. R. Petit, J. Jouzel and M. Stievenard, Distribution of stable isotopes in
surface snow along the route of the 1990 International Trans-Antarctica
Expedition. J. Glaciol., 40, 107-118, 1994.
Raymond, C. F. and K. Tusima, Grain coarsening of water-saturated snow. J.
Glaciol., 22, 83-105, 1979.
Robin, G. de Q. (1983). Ice sheets: isotopes and temperature. InThe climatic
record in polar ice sheets. ed. by Robin, G. de Q., 1-19, 1983.
Satake, H. and K. Kawada, The quantitative evaluation of sublimation and the
estimation of original hydrogen and oxygen isotope ratios of a firn core at East
Queen Maud Land, Antarctica. Bull. Glacier Res., 15, 93-97, 1997.
Satow, K. and O. Watanabe, Net accumulation and oxygen isotope composition of
snow on Mizuho Plateau, Antarctica. Ann. Glaciol., 6, 300-302, 1985.
Sommerfeld, R. A., I. Friedman, and M. Nilles, The fractionation of natural
isotopes during temperature gradient metamorphism of snow. InSeasonal
snow cover: Physics, Chemistry, Hydrology. ed. by Jones, H. G. and
Orville-Thomas, 95-105, 1987.
74
73
Souchez, R. A. and J. Jouzel, On the isotopic composition in D and
18
O of water
and ice during freezing. J. Glaciol., 30, 369-372, 1984.
Suzuki, K., Oxygen-18 of snow meltwater and snow cover. Seppyo, 55, 335-342,
1993.
Thompson, L. G., E. Mosley-Thompson, J. F. Bolzan and B. R. Koci, A 1500-year
record of tropical precipitation in ice cores from the Quelccaya Ice Cap, Peru.
Science, 229, 971-973, 1985.
Thompson, L. G., X. Wu, E. Mosley-Thompson and Z. Xie, 1988, Climatic
records from the Dunde Ice Cap, China. Ann. Glaciol., 10, 1-5, 1988.
Vimeux, F., V. Masson, J. Jouzel, M. Stievenard, and J. R. Petit,
Glacial-interglacial changes in ocean surface conditions in the Southern
Hemisphere. Nature, 398, 410-413, 1999.
Wakahama, G., The metamorphism of wet snow. IAHS Publication, 79, 370-379,
1968.
Watanabe, O., Y. Fujii, K. Kamiyama, H. Motoyama, T. Furukawa, M. Igarashi, M.
Kohno, S. Kanamori, N. Kanamori, Y. Ageta, M. Nakawo, H. Tanaka, K.
Satow, H. Shoji, K. Kawamura, S. Matoba and W. Shimada, Basic analyses of
Dome Fuji deep ice core, Part I: Stable oxygen and hydrogen isotope ratios,
major chemical compositions and dust concentration. Polar Meteorol. Glaciol.,
13, 83-89, 1999.

55
75
Tritium in precipitation and surface waters
77
Chapter 5


5.1 Measurement of tritium

Tritium is a radioactive isotope of hydrogen and it decays to stable helium-3
by emitting beta particle with a half-life of 12.3 years.
Tritium can be measured by a liquid scintillation counter. At present, tritium
concentration in both precipitation and surface water is as low as 0.5-1 Bq/L. For
precious measurement of tritium, electrolytic enrichment of tritium more than 10
times is recommended prior to the measurement by a liquid scintillation counter.
In Fig. 5.1, a typical electrolytic cell including electrode is shown.

Fig. 5.1 A cell for electrolysis. From Satake and Takeuchi (1991).
Chapter5
78
When water is electrolyzed to hydrogen and oxygen, tritium, the heaviest
isotope of hydrogen, strongly enriches in water phase rather than in hydrogen gas.
Tritium separation factor between water and hydrogen, beta, is expressed as
follows,
= (T/H)
water
/ (T/H)
hydrogen

For tritium enrichment, various metals such as platinum, iron, nickel and stainless
steel have been used as an electrode (Florkowsky, 1981: Kitaoka, 1981). The
tritium separation factor is different among anode metals. In Fig. 5.2, histograms
of the separation factor for Fe-Ni and Ni-Ni electrodes are shown. It is easily
observed that the separation factor for Ni-Ni electrode is 5-20 with a broad
distribution. On the contrary, it is 20-25 for Fe-Ni electrode with a sharp
distribution and is systematically higher than that for Ni-Ni electrodes. Platinum
and stainless electrodes show the separation factor almost similar to that of Ni
electrodes (Kitaoka, 1981). Hence, iron reveals high tritium separation factor
among these anode metals. Therefore, iron electrode is recommended for tritium
enrichment. Using Fe-Ni electrode, tritium concentration enriches about 25 times
when water volume was reduced to 1/30. During electrolysis, hydrogen and
oxygen mixture is released from an electrolysis cell. As this gas mixture is very
dangerous, ventilation must be provided during the electrolysis.

Fig. 5.2 Frequency distribution of the tritium separation factor for the Ni-Ni and
Fe-Ni electrodes. From Satake and Takeuchi (1991).
79
To know the tritium enrichment factor, T
f
/T
i
, after the electrolysis, the
following method is commonly used.

1. A simultaneous electrolysis of tritium spiked water having known amount of
tritium with sample water.
2. The measurement of Deuterium before and after electrolysis, i.e., T
f
/T
i
can be
calculated using following equations,

=(D/H)
water
/(D/H)
hydrogen

log(V
i
/V
f
)= /( -1)log(D
f
/D
i
)= /( -1)log(T
f
/T
i
)
log /log =1.4

Recently, a new apparatus for electrolytic enrichment of tritium is developed
(Saito et al., 1996). In this apparatus, solid polymer electrolyte is installed.
Therefore, the addition of electrolyte before electrolysis (e.g., Na
2
O
2
) which is
inevitable for the conventional method, is not needed. Further, hydrogen and
oxygen gases are exhausted separately. Relative to the conventional electrolysis
method, this new apparatus has largely improved in operation and is safe though it
has relatively low of 10-15 due to stainless steel electrode.
To measure low levels of tritium, it is recommended to use a low-background
type liquid scintillation counter which is equipped with an anti-coincident counter
and lead shield that largely reduces back ground of cosmic ray origin. After the
preparation of samples by mixing water sample with liquid scintillator, each
sample and back ground is counted in tritium channel for 500-1000 hours. After
T-channel counting, external standard channel ratio (ESCR) is measured to obtain
counting efficiency. Quenching standards with known amount of tritium are also
measured for T-channel counting and ESCR.
The tritium concentration is given by following equations,

T (Bq/L) = dpmX100X1000/E/V/M/60
T (TU) = dpmX100X1000/E/V/M/60/0.12

where, dpm = SAMPLEcpm - BGcpm

E: efficiency (%)
Chapter5
80
V: sample volume
M: tritium enrichment factor

In a field of hydrology, tritium unit (TU) or tritium ratio (TR) is popularly used as
unit of tritium concentration as well as Bq/L. The relationship between TU, TR
and Bq/L is as follows,

1 TU = 1 TR = 1T/10
18
H = 0.12Bq/L

In this chapter, tritium unit, TU, is used for expressing tritium concentration.

5.2 Tritium in precipitation

In the upper layer of the atmosphere on the earth, cosmic rays, mainly proton
and alpha particles, crush nitrogen and oxygen to produce one or several nucleons.
Then secondary neutrons produced during this process react with nitrogen, oxygen
and water vapor and forms tritium in following nuclear reactions,

14
N(n,
12
C)T,
16
O(n,
14
O)T and
2
H(n, gamma ray)T
Production rate of tritium in the atmosphere is estimated to be
2500atoms/m
2
/s (troposphere: 840, stratosphere: 1660) (UNSCEAR, 1982).
Tritium, thus, produced is oxidized to HTO and falls to the surface of the earth.
The amount of tritium in whole earth is estimated to be 1.3x10
18
Bq (UNSCEAR,
1982). Before thermo nuclear tests, tritium concentration in surface water on land
is found to be 2-8TU (0.2-0.9Bq/L) whereas 1TU (0.1Bq/L) in the surface ocean.
In Fig. 5.3, monthly tritium concentration observed at Ottawa (Canada),
Tokyo and Ryori (Japan), Jakarta (Indonesia) and Kaitoke (New Zealand) as
follows (IAEA, 2001). Tritium concentration at Ottawa, Canada is mostly
20-60TU in 1954 to 1956. Then it rapidly increased with time up to about 6000TU
in 1963. After 1963, it gradually decreased to about 20-30TU in 1990's. The
similar temporal variation with a tritium peak in 1963 is also observed at Tokyo
and Ryori, Jakarta and Kaitoke. The rapid increase in tritium concentration in
precipitation was resulted by thermo nuclear tests that one repeatedly conducted
during 1952-1962. During this period, artificial tritium of 236x10
18
Bq is released
into the nature. This amount is 181 times that of natural tritium in the earth. After
the decrease of thermo nuclear tests in the atmosphere in 1962, tritium content
gradually decreased.

14
N(n,
12
C)T,
16
O(n,
14
O)T and
2
H(n, gamma ray)T
2500atoms/m
2
18
Bq (UNSCEAR,
18
Bq is released
2500atoms/m
2
18
Bq (UNSCEAR,
18
Bq is released
81
Chapter5
82

Fig. 5.3 Monthly tritium concentration in precipitation at Ottawa (A), Tokyo and
Ryori (B), Jakarta (C) and Kaitoke (D) during 1950's to 1990's. Data from
IAEA (2001).

As described above, tritium variation with time is almost similar among
stations in the world. However, it is also observed that tritium concentration is
largely different among these stations even at same time and shows strong positive
correlation with the altitude in Northern Hemisphere. This is because three fourth
83
(183x10^18Bq) of total amount of artificial tritium (243x10
18
Bq) is released from
thermonuclear tests in to the atmosphere in the high latitudes of Northern
Hemisphere (50-75N).
In 1990's, tritium concentrations at these stations seems to be flattened out.
This suggests that the contribution of artificial tritium disappeared from
precipitation in 1980's. Tritium content, however, is still different among those
stations in 1990's, for example, Ottawa: 10-30TU, Ryori: 3-8TU, Jakarta: 2-3TU,
Kaitoke: 2-3 and Hally Bay (Antarctica): 6-20TU (IAEA, 2001). This suggest that
precipitation in higher latitudes has higher tritium concentrations in both
hemisheres. The formation rate of tritium depends on cosmic rays produced by
neutron flux. The neutron flux is four times greater in the polar region than in the
equitorial region. Therefore, tritium production rate and consequently tritium
concentration in the atmosphere is expected to be higher in the polar region. This
is the reason why tritium concentration is higher in higher latitudes even after the
artificial tritium is disappeared.
Tritium concentration in precipitation increases in late winter to spring. This
is called "spring peak" and is induced by the exchange of tropospheric air mass
having high tritium concentration with stratospheric air mass in spring season (Gat,
1980).
As stated above, we can determine the time of deposition of firn from the
tritium variation pattern in precipitation. This method is very popular for dating
ice core in polar region such as Antarctica (e.g., Jouzel et al., 1979; Satake et al.,
1986). This method is still useful in high mountain regions in middle latitudes
such as Japan. In Tateyama high mountain region, located in northern central
Japan, there is a large ice body, called Kuranosuke firn, with the thickness of about
20m at 2800m asl. Figure 5.4 gives the vertical profile of tritium concentration in
ice body. A tritium peak with 143TU was observed at 14m height. The firn at 14m
was inferred to deposit in the first half of 1960's.
10
18
Bq) i
|5075^).
Chapter5
84

Fig. 5.4 Vertical profile of tritium concentration in Kuranosuke firn. From
Satake and Kanda (1989).

5.3 Tritium in river and ground water

Tritium concentration in river water and ground water increased after the
beginning of thermonuclear test and become larger than that of precipitation after
the end of aerial thermonuclear tests (Fontes, 1981). Figure 5.5 shows the monthly
tritium concentration as well as precipitations during 1980 to 1987 in Jinzu River
water, Toyama in north central Japan. It is clearly observed that Jinzu River has
higher tritium content than the precipitation, and also observed that the difference
between tritium content and precipitation in Jinzu River is decreased with time due
to relatively rapid tritium decrease from about 30TU in 1980 to 13TU in 1987.
85

Fig. 5.5 Monthly tritium concentration in Jinzu river water and precipitation at
Toyama during 1980 to 1988.

In ground water, tritium concentration can be varied from place to place even
in a small area. Tritium concentration in ground water in Toyama (10km x 10km)
observed in 1987 is depicted in Fig. 5.6. In this area tritium concentration ranges
from lower than 2TU to more than 30TU. From the tritium distribution map, it is
observed that tritium concentration in southern area is 10-12TU and increases
towards north up to more than 30TU. Then it decreases steeply to 10TU and
finally to < 2TU in coastal region. In Toyama, the ground water flows from south
to north. Thus, the variation in tritium concentration in the ground water represents
the temporal variation of tritium in precipitation. Tritium content in southern
area (10-12TU) is almost same to that of precipitation in 1987 (8-12TU). Ground
water having tritium content more than 30TU, which is the highest concentration
in this area, can be regarded to be contributed by precipitation in the first half of
1960's when tritium content was the highest. The ground water in the coastal
region with lower than 2TU is clearly derived from meteoric water in pre-bomb
age before 1950s. Thus we can conduct the dating of ground water from the
tritium distribution map.
Chapter5
86

Fig. 5.6 A map showing tritium concentration in ground water in Toyama.

After 1988, tritium concentration in river and ground water decreased and
estimated to be 4-5TU in river water and 0-5TU in ground water in and around
Toyama in 1998-2000.
For precious dating of ground water, tritium-helium 3 method is
recommended (Tolstikhin and Kamenskiy, 1969). In this method, both the tritium
and helium-3 concentrations in ground water are measured. Tritium concentration
in precipitation, that is the source of the ground water can be obtained from the
sum of tritium and helium-3 in the ground water. So, the date of ground water can
be done using the following equation.

87
N=N
0
exp(-t)
N: tritium concentration in the ground water
N
0
: sum of tritium and helium-3 concentrations in the ground water

References

Florkowski, T., Low level tritium assay in water samples by electrolytic
enrichment and liquid scintillation counting in the IAEA laboratory, Methods
of low-level counting and spectrometry, 335-351, IAEA, Vienna., 1981.
Fontes, J.C., Environmental isotopes in groundwater hydrology, Handbook of
environmental isotope geochemistry, 75-140, Elsevier, Amsterdam, 1980.
Gat, J.R., The isotopes of hydrogen and oxygen in precipitation, Handbook of
environmental isotope geochemistry, 21-47, Elsevier, Amsterdam, 1980.
International Atomic Energy Agency, http://www.isohis.iaea.org/, 2001.
Jouzel, J., M. Lorius and L. Merlivat, Artifical tritium fall-out at the South Pole,
Behaviour of tritium in the environment, 31-46, IAEA, Vienna, 1979.
Kitaoka, K., On the electrolytic separation factor of tritium, Radioisotopes, 30,
247-252, 1981. (in Japanese)
Saito, M., S. Takata, T. Shimamune, Y. Nishiki, H. Shimizu and T. Hayashi,
Tritium enrichment by electrolysis using solid polymer electrolyte,
Radioisotopes, 45, 3-10, 1996. (in Japanese)
Satake, H. and Y. Kanda, Tritium and stable isotope geochemistry of the
Kuranosuke snow patch, Central Japan, Annual Rept. Tritium Res. Center
Toyama Univ., 9, 107-119, 1989. (in Japanese)
Satake, H. and S. Takeuchi, Electrolytic enrichment of tritium with Fe-Ni and
Ni-Ni electrodes and estimation of tritium enrichment factor using Fe-Ni
electrodes, Geochem. J., 35, 429-435, 1991.
Tolstikhin, I. and L. Kamenskiy, Determination of groundwater ages by the T-3He
method, Geochem. Internat., 6, 810-811, 1969.
United Nations Scientific Committee on the Effects of Atomic Radiation 1982,
1982, 1982 report "Ionizing radiation: Sources and biological effects", United
Nations, New York.

Stable Isotopic Composition in Soil Water
89
Chapter 6


6.1 Introduction

6.1.1 Fundamentals of rainfall-runoff processes in headwater catchment

An overview of isotopic tracer approach of rainfall-runoff processes at the
catchment scale will be discussed in this section. The water budget is the key for
investigating the water resources, chemical properties and runoff generation
mechanism in the headwater catchments (Fig. 6.1). The water balance in a catchment
is shown in the following equation,

P R ET = S (6.1)

where P is the input consisting of precipitation in solid and liquid forms, R is the
runoff, ET is the evapotranspiration, and S is the changes in storage. Generally,
annual evapotranspiration corresponds to 40 to 50 % of the annual precipitation in the
forested headwater catchment of the warm humid regions. Therefore, half of the
annual precipitation discharges as stream and subsurface flow from the catchment.
Also, the infiltration rate of the precipitation into the soil surface is estimated to be
more than 200 mm/h in the forested catchment of the humid regions, and there are few
cases that rainfall intensity exceeds 200 mm/h in the warm humid regions.
Consequently, about half of the annual precipitation moves as subsurface water
including in soil and ground waters, and the subsurface water has an important role in
rainfall-runoff processes in the forested headwater catchment.
In rainfall-runoff process, streamflow generation is a key component of the
hydrological cycle, and the stable isotopes such as deuterium and oxygen 18 have been
used as effective tracers for elucidating the source or component of the runoff water
during the rainstorms. It is well known that the isotopic composition of rainfall varies
from storm to storm at a given site and thus the rainfall in any of the storm may differ
isotopically from the subsurface water stored within the catchment before the
Stable isotopic composition in soil water

here P is lhe inpul consisliny oI precipilalion in soIid and Iiquid Iorms, R is lhe
Chapter 6
90

beginning of the storm (Genereux and Hooper, 1998). This greater temporal variability
in the isotopic composition of rainfall relative to that of the subsurface water enable us
to use the following mass balance and mixing equations for separating the storm
hydrograph into event (rainfall) and pre-event (subsurface water) components (Buttle,
1998).

Q
t
= Q
p
+ Q
e
(6.2)
C
t
Q
t
= C
p
Q
p
+ C
e
Q
e
(6.3)

where Q is discharge rate, C is the isotopic ratio, and suffix t, p and e are the total
runoff water, the pre-event water and the event water components, respectively. By
combining these equations, the following equation is given,

Q
o
= [(C
t
C
e
) / (C
p
C
e
)] Q
t
(6.4)

Therefore, the ratio of pre-event water component to the total runoff rate is
estimated by observing runoff rate, and isotopic compositions of stream water, rainfall
water and subsurface water. For using this method, the following conditions should be
satisfied (Sklash and Farvolden, 1979);
1) The isotopic ratio of the event component is significantly different from that of
the pre-event component.
2) The event component maintains a consistent isotopic ratio.
Fig. 6.1 Schematic illustration showing hydrological (rainfall-runoff) cycle in the
headwater catchments.
Runoff
Time
Precipitation Evapotranspiration
Subsurface water
Runoff
Time
Precipitation Evapotranspiration
Subsurface water
Runoff
here Q is discharye rale, C is lhe isolopic ralio, and suIIixes l, p and e are lhe lola
91
3) The groundwater and soil water are isotopically equivalent or soil water
contributions to runoff are negligible due to hydrogeologic constraints.
4) Surface storage contributes minimally to the runoff event.

Based on this method, many calculations for hydrograph separation were
performed mainly in mid and high latitude regions. In almost all cases, pre-event water
accounts for over half (and usually about three-quarters) of the runoff and/or peakflow
associated with rainstorms (Genereux and Hooper, 1998; Tsujimura and Tanaka, 1996).
Consequently, the pre-event (subsurface) water dominates the runoff even during the
time scale of rainstorms in the forested headwater catchments of the warm humid
regions (Fig. 6.2).
However, McDonnell et al. (1990) showed that the temporal variation of isotopic
ratio in the event water is not always negligible in relation to the assumption (2). Also,
Kendall and McDonnell (1993) and Tsujimura and Tanaka (1998) showed that the
assumption (3) is not always satisfied in the headwater catchments. Temporal and
spatial variations of stable isotopic compositions in the subsurface water along with the
subsurface flow have not been clarified enough in the catchments of any regions.

Fig. 6.2 Tracer separation examples (Hooper and Shoemaker, 1985).
ralio in lhe eVenl aler is nol aIa,s neyIiyibIe in reIalion lo lhe condilion2).AIso,
condilion 3) is nol aIa,s salisIied in lhe headaler calchmenls. JemporaI and
Chapter 6
92
6.1.2 Physical processes of soil water movement

Soil consists of three phases (Fig. 6.3); they are liquid phase, solid phase and
gaseous phase. Soil water content (liquid phase) is described by the ratio of the liquid
phase to the total volume of the soil as follows,

= (V
w
/ V) 100 (%) (6.5)

where is the volumetric water content, V
w
is the volume of liquid phase (water),
and V is total volume of the soil sample.
Soil water content can be measured by many methods, and outline of three typical
methods; are namely gravimetric, neutron scattering, and time domain reflectrometry.
In gravimetric method the soil is actually sampled and the sample is weighted, dried in
an oven, and weighted again after drying (Hanks, 1992). Thus the water mass
associated with the dry soil mass can be determined. This method has the advantage as
it is direct, whereas it has the disadvantage that it destroys the soil at the sampling site.
The neutron scattering method is based on the principle that fast neutrons emitted from
a radioactive source are slowed down or thermalized when they encounter hydrogen in
the soil, and most of the hydrogen in the soil is associated with soil water (Bell and
McCulloch, 1969). In time domain reflectrometry (TDR) method, the transit time of an
electrical signal along metallic probes are calculated (Topp et al., 1982). This time is
closely related to the dielectric constant of the material surrounding the probe, and
found that the dielectric constant of liquid water is much higher than the soil solids.
Thus the constant measured can be related to the soil water content.

Volume Weight
Air (gas)
Water
(liquid)
Soil
(solid)
Volume Weight
Air (gas)
Water
(liquid)
Soil
(solid)
Fig. 6.3 Three phases in soil.
93

Generally, the change of water storage; S (in Eq. 6.1) is negligible in annual
water budget, however, the S has an important role in the seasonal water budget.
Hudson (1988) estimated the role of S in the seasonal water budget by measuring soil
moisture content using neutron scattering method in Plynlimon catchment consisting
of peat and podzolic soils, mid Wales, UK. Figure 6.4 shows temporal change of soil
water content observed at some sites in the Plynlimon catchment from 1974 to 1982. In
Fig. 6.4 Soil moisture variation observed under the various vegetation conditions in
UK (Hudson, 1988).
S
S
S
Chapter 6
94
Fig. 6.4 soil moisture deficit is defined as difference from the mean value at each site
for the winter 1974/1975. The soil moisture deficit in the coniferous forest tends to be
lower than that in the short grass and heath, and it should be noting that the soil
moisture does not recover quickly after the dry summer in 1976. This shows that the
change of soil water content is not negligible especially in the seasonal water budget.
Soil water movement is governed by soil water potential. Expressing the
potentials in units of head (cmH
2
O), the total potential (hydraulic head) (h) is, for most
practical purposes, taken as the sum of the matric potential (pressure head) () and the
gravitational potential (gravitational head) (z) (Freeze and Cherry, 1979).

h = + z (6.6)

The gravitational head (z) is difference of elevation from the reference level
(datum), and the pressure head is expressed by water pressure. The pressure head ()
of the soil water above the groundwater table shows negative value, whereas
groundwater below the water table shows positive value. Thus the pressure head at the
water table equals to atmospheric pressure, i.e. 0 cmH
2
O. Soil water will move from
regions of high to lower hydraulic head.

6.2 Soil water extraction techniques

6.2.1 Suction method

Suction lysimeter/sampler is generally used for soil water sampling by suction
method. Suction lysimeter consists of a porous cup of 17 mm in diameter, a glass
collecting bottle and a connecting tube of 2 mm in diameter (Fig. 6.5). The porous cup
is installed at a depth where the soil water is sampled. A small hand pump is connected
to the bottle and a suction pressure of 60 to 70 kPa is applied in the bottle and tube.
The soil water is drawn in through the porous cup and collected in the bottle. This
method has advantages that the soil layer is not destroyed when the water is sampled
and the water sample can be taken repeatedly from the same site and depth. The
disadvantage is that the sampling is impossible under the dry soil moisture condition,
and the sampling is difficult at a site of high elevation with low atmospheric pressure.
Stewart and McDonnell (1991) stated that the suction lysimeter does not have
significant affect on isotopic ratio in soil water.

95

6.2.2 Centrifugation method

Soil sample should be taken from the field for centrifugation and distillation
methods. Change of isotopic composition in soil water should be cared along with the
soil sampling (Shimada, 1996). Especially, water must not be used for soil core
sampling, and time of soil sample exposed to the atmosphere must be minimized.
Simple sampling method is that the soil is sampled using hand auger, and packed in the
bag made of vinyl. This sampling method can maintain enough accuracy for isotopic
analysis (Shimada, 1996).
Centrifugation method generally can be used for sampling the soil water in which
the pressure head is over 10000 cmH
2
O (< pF 4.0). This method has advantage that
the soil water can be sampled at some different pressure heads, and the procedure is
very simple. Figure 6.6 shows schematic diagram of the standard centrifugation device.
The rotation rate (n; rpm) of the device is related with the pressure head of soil water
(
s
; cmH
2
O) in the sample as given below (Fig. 6.6),

log
s
= 2 log n + log h + log (r
0
h/2) 4.95 (6.7)

It takes about two hours generally for taking the water with volume of a few to 10
mL at a pressure head. There is a disadvantage for this method that the soil water is not
sampled below the pressure head of 10000 cmH
2
O.
Fig. 6.5 Schematic illustration showing devices to sample soil water (suction
lysimeter) and rain water (throughfall and stemflow) (Tsujimura, 1994).
Chapter 6
96

6.2.3 Distillation method

In distillation method, it is necessary that all water in the soil sample must be
taken because procedure of this method accompanies with the phase change of the soil
water. Also, this method has an advantage that a large quantity of water can be
extracted even under the dry soil moisture condition.
Figure 6.7 shows an example of vacuum distillation system by Saxena (1987).
The soil core samples are placed in desiccation chambers fitted with heating elements,
which are temperature-regulated by a relay. Each desiccation chamber is connected to
two glass vapor traps, and the glass traps are evacuated before their placement in a
cooling chamber containing alcohol kept at 60 C by a compressor. During
evacuation of the traps, the desiccation chambers are kept closed by a valve.
Approximately 20 minutes are needed to cool down the traps, and at this stage the
chambers are slowly opened and heating is started. It takes approximately 5 hours to
remove all moisture from the soil cores. Saxena (1983) mentioned that recovery of
moisture is almost 100 % and no fractionation of oxygen 18 occurs during storage and
extraction.
Porous plate
Free water
Soil sample
Filter paper
Cap
Can
Rotation shaft
Porous plate
Free water
Soil sample
Filter paper
Cap
Can
Rotation shaft
Fig. 6.6 Schematic diagram showing centrifuging device.
remoVe aII moislure Irom lhe soiI cores. Saxena and ressie
|J983)menlioned lhal recoVer, oI moislure is aImosl J00 and no
Iraclionalion oI ox,yen J8 occurs duriny sloraye and exlraclion.
97
Figure 6.8 shows an apparatus of vapor pressure distillation method by Shimada
et al. (1978). To prevent the vapor water of the air in the line is collected, the pressure
of the line is depressed at 0.1 atm, and then the dry air is installed within the line. After
filling the dry air in the line, soil sample is kept at 110 C and the distilled soil water is
collected using Liebig cooling pipe. Shimada et al. (1978) showed that recovery of the
moisture ranged from 95 to 102 %.

Fig. 6.8 Apparatus of vapor pressure distillation method (Shimada et al., 1978).
Fig. 6.7 Schematic diagram showing distillation device (Saxena, 1987).
Chapter 6
98
Figure 6.9 shows an azeotropic distillation apparatus by Revesz and Woods
(1990). The principle of this method involves the formation of an azeotropic mixture of
toluene with water at 84.1 C but floats on top of the water at room temperature. The
boiling point of toluene-water azeotrope is 84.1 C, significantly lower than that of
water (100 C) and toluene (110 C). The receiving funnel has a side-arm at an angle
of about 105, and this angle allows the toluene to overflow to drip back into the flask
without clogging the funnel. Enough toluene is added so that the soil remains covered
throughout the entire distillation process. At the beginning of the distillation, water and
toluene distill together, causing a cloudy apparatus. The distillation should continue
until the liquid turns clear in the funnel. It is crucial that the distillation should be
continued 10 to 15 minutes after the first clear drops begin to appear in the funnel.
Revesz and Woods (1990) showed that the recovery of the moisture is almost 100 %.
Walker and Woods (1991) reported on an interlaboratory comparison of soil water
extraction techniques (azeotropic, vacuum, microdistillation, and centrifugation
methods) obtained from 14 laboratories. The results showed a large variation (of up to
30 for deuterium and 3.4 for oxygen 18) in the isotopic composition of extracted
water, and the variation would be correlated with the final extraction temperature, and
was ultimately associated with incomplete extraction.

Fig. 6.9 Apparatus of azeotropic distillation method (Revesz and Woods, 1990).
99
6.3 Processes leading to isotopic variations in soil water

6.3.1 Meteorological inputs

Detail on the formation processes of stable isotopic composition in precipitation is
described in Chapter 3. The schematic diagram is shown in Fig. 6.10 representing the
stable isotopic variation process of water near the soil surface. The stable isotopic
compositions of soil water are primarily determined by those of rain water.
In the forest regions rainfall is transformed into throughfall and stemflow. Figure
6.11 shows a relationship of monthly
18
O between rainfall outside the forest and
throughfall observed at two sits in a forested headwater basin, namely Kawakami,
Nagano Prefecture, central Japan. The volume weighted mean
18
O in throughfall is
0.4 higher than that in rainfall water, and this shows that the water enrichment
would occur along with the interception loss by the tree canopy.

Soil surface
Groundwater table
c
p
Cloud
Precipitation
Condensation
Infiltration
s Soil water
Isotopic mixing at
Zero Flux Plane
Evaporation
Groundwater recharge
g Groundwater
Transpiration
Water flow path
without isotopic
fractionation
Water flow path with
isotopic fractionation
or variation
Soil surface
Groundwater table
c
p
Cloud
Precipitation
Condensation
Infiltration
s Soil water
Isotopic mixing at
Zero Flux Plane
Evaporation
Groundwater recharge
g Groundwater
Transpiration
Water flow path
without isotopic
fractionation
Water flow path with
isotopic fractionation
or variation
Fig. 6.10 Schematic diagram showing variation processes of stable isotope in
water near the soil surface.
Chapter 6
100

Figure 6.12 shows the temporal change of
18
O in throughfall (as an input to the
soil surface), soil water and groundwater observed in Kawakami basin from May to
November, 1991. The oxygen 18 values in soil water at the depth of 10 to 50 cm are
affected considerably by the values of throughfall, whereas those of soil water does not
change. This shows that the effect of the input water on the soil water oxygen 18
values causes to the depth of approximately 50 cm, and an isotopic homogenization
process would occur in the soil water at the depth of 50 to 70 cm. The homogenization
processes will be mentioned later.
Fig. 6.11 Relationship of monthly 18O between rainfall outside the forest and
throughfall observed in a headwater catchment in Japan (Tsujimura,
1994). Open circles: Oak forest, Solid circles: Japanese larch forest
Japanese larch
Oak
Japanese larch
Oak
o s
101

6.3.2 Evaporation

The effect of evaporation on the stable isotopic composition of soil water has been
previously explained well by some scientists (e.g. Barnes and Allison, 1983; 1984;
Allison et al., 1983; Barnes and Turner, 1998). Many of them discussed the
evaporation process under the relatively dry conditions, however, we do not have
Fig. 6.12 Temporal variation of
18
O in throughfall, soil water, groundwater and
stream water observed in Japanese larch forest in a headwater
catchment in Japan (Tsujimura, 1994).
Chapter 6
102
enough information on the relation between the isotopic composition of soil water and
evaporation under the warm humid regions.
Tsujimura and Tanaka (1998) discussed the effect of evaporation from the soil
surface on the stable isotopic ratio of subsurface water in a forested headwater
catchment, central Japan. They monitored the stable isotopic composition in rainfall,
throughfall, soil water at multiple depths, groundwater and stream water for
approximately two years. Figure 6.13 shows a -diagram for soil water at the depths
from 10 to 200 cm collected from April to November, 1991. All data of soil water fall
on the local meteoric water line with the slope of approximately 8. It is also clear in
this figure that while the data relating to shallow soil water 10 to 70 cm in depth shows
both a large variation and a D difference between the maximum and minimum values
of approximately 68 , values of deep soil water greater than 100 cm in depth
converge on a value which is a little higher than the volume weighted mean of
throughfall data. This result suggests that an isotopic homogenization of soil water
might be occurring between the soil surface and a depth of 100 cm in the Kawakami
Basin. Also, Tsujimura and Tanaka (1998) showed that the mean
18
O of deep soil
water below 100 cm is 0.24 higher than the volume weighted mean of throughfall,
and considered that the difference in value would be explained by the evaporation
process from the soil surface, because no isotopic fractionation occurs in the absorption
of water by the root systems. They estimated the evaporation rate from the soil surface
in the Kawakami basin using the following eqation,

lr
-
li
= 10
3
(1 / - 1) ln f
l
(6.8)

where is the value of the water, the suffixes lr and li represent remaining water
(deep soil water) and initial water (throughfall), respectively, and f
l
is the fraction of
remaining water. Using a value of -12.41 for
li
, representing the volume weighted
18
O mean of throughfall, a value of -12.17 for
lr
, representing the mean
18
O of
soil water below a depth of 100 and a value of 1.011 for the fractionation factor, then
the equation (6.8) yields a value of 0.97. Consequently, it can be reasonably stated that,
on average, 3 % of bulk throughfall might be evaporated from the soil surface in the
Kawakami Basin. Tsujimura and Tanaka mentioned the this procedure seems to be
appropriate to discuss the evaporation rate from the soil surface under some conditions:
1) a preferential flow through macro pore is not predominant in the soil, 2) the stable
isotopic ratio of soil water is homogenized at a certain depth and 3) the homogenized
isotopic ratio of soil water represents a value which is affected by the evaporation and
mixing processes of soil water.
lhe Lq. |6.8) ,ieIds a VaIue oI 0.97. ConsequenlI,, il can be reasonabI, slaled lhal,
103

6.3.3 Percolation, groundwater recharge and runoff

The formation process of stable isotopic compositions in soil water has not been
well understood in the warm humid regions (e.g. Darling and Bath, 1988). Generally,
the stable isotopic ratio in shallow soil water is relatively responsive to that in rainfall,
however deeper soil water and water near the stream subject to occasional water table
rises shows much less variation (Stewart amd McDonnell, 1991), as mentioned
previously. The stable isotopic homogenization mechanism has not been enough
investigated throughly.
Tsujimura and Tanaka (1998) discussed the variation in process of stable isotopes
in soil water (shown in Fig. 6.14) using the tensiometric data observed at the same sites
and depths for suction lysimeters.
Fig. 6.13 -diagram of soil water at the depths from 10 to 200 cm in a headwater
catchment (Tsujimura and Tanaka, 1998).
Chapter 6
104

Figure 6.14 shows an isopleth diagram of the soil water hydraulic head computed
using daily mean values of the pressure head observed at intervals of 30 minutes at A
and C sites in Kawakami basin from August to September, 1991. From this figure, an
inference can be made regarding the nature of soil water movement during periods
when rainfall was present or absent. The divergent zero flux plane appears at the soil
surface immediately after the rainfall and fell to the depth of approximately 100 cm.
The divergent zero flux plane exists at a depth between 70 and 100 cm and upward soil
water movement was predominant above this plane during the rainless periods. With
Fig. 6.14 Isopleth diagram of the soil water hydraulic head and hydraulic head
profiles versus depths observed in summer season (Tsujimura and
Tanaka, 1998). A site: Japanese larch forest; C site: Oak forest. o
105
onset of a rainfall event, a convergent zero flux plane occurs at the soil surface. The
convergent zero flux plane falls to the depth of the divergent zero flux plane with
penetration of wetting front. Finally, the convergent and divergent zero flux planes
disappear and downward soil water flow is observed throughout the soil layer. It is
especially worth mentioning that the convergent and divergent zero flux planes are
observed frequently above a depth of 100 cm. At the depth of the convergent zero flux
plane, infiltrating water should mix with stored soil water. Therefore, the isotopic
homogenizing process of soil water should occur from the soil surface to a depth of
100 cm with movement of the convergent zero flux plane. Consequently, there is little
change in the value of soil water below a depth of 100 cm. Tsujimura and Tanaka
(1998) focused on the behavior of zero flux plane as a cause of stable isotopic
homogenization in the soil water. Also, a dispersion process of isotope molecular in the
soil water should be important in considering the isotopic homogenization mechanism
as shown by Shimada (1988).

6.4 Future directions

The stable isotope variation process in the soil water has been comparatively well
studied for the evaporation process at the laboratory scale (Barnes and Turner, 1998).
However, the effect of infiltration, percolation, and recharge process on the distribution
of stable isotope of the subsurface water is not enough understood at the field scale.
Also, stable isotopic process of water in soilplantatmosphere continuum system has
not been investigated throughly in the field. Stable isotope is very effective tracer
indeed for water circulation process, however, it does not produce enough information
alone. Physical data, such as tesiometric, hydrometric, and atmospheric data should be
combined with the stable isotope data to understand the water and energy flow process
near the soil surface including the subsurface flow process in the field scale. It would
be necessary that a research project should be processing for those objectives
cooperation of hydrological, atmospheric, and ecological scientists.

References
Allison, G. B., Barnes, C. J. and Hughes, M. W. (1983): The distribution of deuterium
and
18
O in dry soils 2. Experimental. Journal of Hydrology, 64, 377-397.
Barnes, C. J. and Allison, G. B. (1983): The distribution of deuterium and
18
O in dry
Chapter 6
106
soils 1. Theory. Journal of Hydrology, 60, 141-156.
Barnes, C. J. and Allison, G. B. (1984): The distribution of deuterium and
18
O in dry
soils 3. Theory for non-isothermal water movement. Journal of Hydrology, 74,
119-135.
Barnes, C. J. and Turner, J. V. (1998): Isotopic exchange in soil water. In Kendall, C.
and McDonnell, J. J. (eds.), Isotope Tracers in Catchment Hydrology, Elsevier,
Amsterdam, 137-163.
Bell, J. P. and Mcculloch (1969): Soil moisture estimation by the neutron method in
Britain. Journal of Hydrology, 7, 415-433.
Buttle, J. M. (1998): Fundamentals of small catchment hydrology. In Kendall, C. and
McDonnell, J. J. (eds.), Isotope Tracers in Catchment Hydrology, Elsevier, 1-49.
Darling, W. G. and Bath, A. H. (1988): A stable isotope study of recharge processes in
the English Chalk. Journal of Hydrology, 101, 31-46.
Freeze, R. A. and Cherry, J. A. (1979): Groundwater. Prentice-Hall, Inc., Englewood
Cliffs, 604p.
Genereux, D. P. and Hooper, R. P. (1998): Oxygen and hydrogen isotopes an
rainfall-runoff studies. In Kendall, C. and McDonnell, J. J. (eds.), Isotope Tracers
in Catchment Hydrology, Elsevier, Amsterdam, 319-346.
Hudson, J. A. (1988): The contribution of soil moisture storage to the water balances of
upland forested and grassland catchments. Hydrological Sciences Journal, 33,
289-309.
Hanks, R. J. (1992): Applied Soil Physics Soil Water and Temperature Applications
Second Edition. Springer-Verlag, New York, 176p.
Kendall, C. and McDonnell, J. J. (1993): Effect of intrastorm isotopic heterogeneities
of rainfall, soil water, and groundwater on runoff modeling. In Peters, N. E. et al.
(eds.), Tracers in Hydrology, IAHS Publ., No. 215, 41-48.
McDonnell, J. J., Bonell, M., Stewart, M. K., and Pearce, A. J. (1990): Deuterium
variations for stream hydrograph separation. Water Resources Research, 26,
455-458.
Revesz, K. and Woods, P. H. (1990): A method to extract soil water for stable isotope
analysis. Journal of Hydorlogy, 115, 397-406.
Saxena, R. K. and Dressie, Z. (1983): Estimation of groundwater recharge and
moisture movement in sandy formations by tracing natural oxygen-18 and injected
tritium profiles in the unsaturated zone. Proceedings of Symposium on Isotope
Techniques in Water Resources Development, IAEA Paper No. IAEA-SM-319/40,
139-150.
Saxena, R. K. (1987): Oxygen-18 fractionation in nature and estimation of
107
groundwater recharge. Report Series, Division of Hydrology, Department of
Physical Geography, Uppsala University, No. 40, 150p.
Shimada, J., Kayane, I. and Tanaka, T. (1978): Methods of soil water collection at
different matric suctions. Japanese Journal of Limnology, 39, 22-28 (in Japanese
with English abstract) .
Shimada, J. (1988): The mechanism of unsaturated flow through a volcanic ash layer
under humid climatic conditions. Hydrological Processes, 2, 43-59.
Shimada, J. (1996): Rainfall Infiltration and Groundwater Recharge 4.2 Estimating
groundwater recharge rate by environmental isotopes. Journal of Groundwater
Hydrology, 38, 205-210 (in Japanese).
Sklash, M. G. and Farvolden, R. N. (1979): The role of groundwater in storm runoff.
Journal of Hydrology, 43, 45-65.
Stewart, M. K. and McDonnell, J. J. (1991): Modeling base flow soil water residence
times from deuterium concentrations. Water Resources Research, 27, 2681-2693.
Topp, G. C., Davis, J. L. and Annan, A. P. (1982): Electro-magnetic determination of
soil water content using TDR: I. Applications to wetting fronts and steep gradients.
Soil Science Society of America Journal, 46, 672-678.
Tanaka, T., Tsujimura, M., Shimada, J., Itadera, K., Nakai, N. and Kusakabe, M.
(1992): Relationship between deuterium and oxygen-18 delta-values of soil water
in humid tropical and humid temperate regions. Annual Report, Institute of
Geoscience, University of Tsukuba, No. 18, 27-32.
Tsujimura, M. (1994): Dynamic behavior of soil water movement in a headwater basin.
Ph. D. Thesis, Doctoral Program in Geoscience, University of Tsukuba, 132p.
Tsujimura, M. and Tanaka, T. (1996): Studies on runoff generation processes using
stable isotopes. In Onda, Y., Okunishi, K., Iida, T. and Tsujimura, M. (eds),
Hydrogeomorphology: Interactions Between Hydrologic Cycle and
Geomorphology in Mountainous Area. Kokonshoin, Tokyo, 7987 (in Japanese).
Tsujimura, M. and Tanaka, T. (1998): Evaluation of evaporation rate from forested soil
surface using stable isotopic composition of soil water in a headwater basin.
Hydrological Processes, 12, 2093-2103.
Walker, G. R. and Woods, P. H. (1991): Inter-laboratory comparison of methods to
determine the stable isotope composition of soil water. Proceedings of Symposium
on Isotope Techniques in Water Resources Development, IAEA Paper No.
IAEA-SM-319/40, 509-517.

Topp, G. C., Davis, J. L. and Annan, A. P. (1982): Electro-magnetic determination of
soil water content using TDR: I. Applications to wetting fronts and steep gradients.
Soil Science Society of America Journal, 46, 672-678.
Tanaka, T., Tsujimura, M., Shimada, J., Itadera, K., Nakai, N. and Kusakabe, M.
(1992): Relationship between deuterium and oxygen-18 delta-values of soil water
in humid tropical and humid temperate regions. Annual Report, Institute of
Geoscience, University of Tsukuba, No. 18, 27-32.
Environmental isotopes in groundwaters
109
Chapter 7


Groundwater is an important source of water for agricultural, industrial,
and domestic uses, and often it may be only source of water supply for the
people in arid regions and developing countries. Although groundwater was
found to be one of the important components in the hydrological cycle,
however, their role is not well understood.
As geochemical tools, stable and radioactive environmental isotopes such
as
2
H,
3
H,
14
C, and
18
O can provide information on the physical and chemical
processes operating on groundwater, on the hydrogeological characteristics of
aquifers including origin, time, and rate of recharge, and on aquifer
interconnections. This kind of information, often can not be obtained other
than isotope techniques, is valuable in the assessment and management of
groundwater resources, especially in the developing countries and the
mountainous areas where there is a scarcity of hydrogeological information
and/or long-term series of observation data are generally missing. In this
chapter, citing a number of case studies, scientific background of application
of environmental isotope techniques to groundwater hydrology is outlined.

7.1 Tracing groundwater with D and O

7.1.1 Where, when, and how groundwater is recharged?

The rainout process in clouds controls the partitioning of isotopes in
precipitation, providing the variable input functions that are effective in
tracing groundwater. The position of local precipitation on the meteoric water
line is controlled by a series of effects: dependence of isotopic composition on
air temperature, or temperature effect (Dansgaard, 1964); continental and
rain-shadowing effects (e.g. Sonntag et al., 1979) depending on vapor mass
trajectories; altitude effect (e.g. Payne and Yurtsever, 1974) which occurs
when a vapor mass rises over the landscape; amount effect (e.g. Dansgaard,
1964) that results in more negative isotopic values with increasing amount of
Chapter 7
110
rain. Each has a characteristic effect on the isotopic composition of
precipitation, which is preserved in groundwater and provides insights into
recharge and flow processes.
Among these effects, the isotope-altitude gradient, or altitude effect, has
turned out to be the most powerful tool for tracing groundwater as it
distinguishes groundwaters recharged at high altitude from those at low
altitude. Such kind of information could not otherwise be obtained. For the
last several decades, the altitude effect has been established over the world
and successfully applied in a number of hydrological studies, even in
watersheds with elevation contrasts of less than a couple of hundred meters
(Clark and Fritz, 1997).
Precipitation gets isotopically lighter with increasing altitude as the
heavy isotopes are depleted more efficiently when clouds rise up to the
mountains. For
O in the European and African continents, the effect varies

between about -0.15 to -0.5 per 100m rise in altitude, with a corresponding
gradient of about -1 to -4 for D (Clark and Fritz, 1997). Scholl et al. (1996)
reported a gradient of -0.07 to -0.32
O and -0.25 to -2.6 D per 100m

altitude for the oceanic islands. Differences in the physiographic and
climatological settings of the respective areas are supposed to be responsible
for this wide range of gradients. The altitude effect, therefore, has to be
determined, in advance, in the respective study areas.
Based on the altitude effect, Yasuhara et al. (1995, 1997) provided a good
example of isotopic tracing of groundwater in Mt. Fuji, 3776-m high volcano,
Japan. Groundwater recharge to Mt. Fuji occurs primarily during summer,
when most of the moisture supply is derived from the Pacific Ocean through
southeasterlies and/or southerlies. As a result, annual precipitation on the
north slope (1500-2000 mm/year), which is on the leeward side with respect
to precipitation air mass trajectories, is less than on the other windward slopes
(2750 mm/year). The research followed the following logical steps:
1. Seasonal precipitation at 9 stations were collected for a year between nearly
sea level and summit: one collector was on the summit, three on the north
slope, and five on the other slopes.
2. They analyzed D in volume-weighted annual mean precipitation samples
from different altitudes and defined separate precipitation lines with quite
different altitude effects for the north and other slopes: -0.8 D per 100 m
altitude for the north slope and -1.4 D per 100 m altitude for the other
slopes (Fig. 7.1). The leeward north slope precipitation is more depleted than
1. Seasonal precipitation at 9 stations were collected for a year between nearly
sea level and summit: one collector was on the summit, three on the north
slope, and five on the other slopes.

111
that on the windward other slopes and the difference in D between the two
precipitation lines is about 17, 10 and 5 at an altitude of 1000, 2000
and 3000 m a.m.s.l., respectively.

Fig. 7.1 Relation between D values and altitude for precipitation
(precipitation line) and groundwaters of known recharge
areas (recharge-water line) on the leeward north and
windward other slopes of Mt. Fuji. is the difference in D
between the precipitation and recharge-water lines at a
given elevation (Yasuhara et al., 1997).
(precipitation line) and groundwaters of known recharge
areas (recharge-water line) on the leeward north and
windward other slopes of Mt. Fuji. is the difference in D
between the precipitation and recharge-water lines at a
given elevation (Yasuhara et al., 1997).
Chapter 7
112
3. Springs and cavern waters, for which reasonable estimates of their origin of
recharge (recharge altitude) can be deduced from hydrogeological and
topographical data, were analyzed for D. Then an isotope-altitude graph
(recharge-water line) was calibrated for each of the slopes (Fig. 7.1), defining
the altitude effects reflected in groundwater: -1.6 D per 100 m altitude for
the leeward north slope and -2.0 D per 100 m altitude for the windward
slopes. The difference in altitude effect for groundwaters between the slopes is
less prominent than that for precipitation.
4. The D values of groundwater samples from springs and wells were plotted
as a function of altitude (Fig. 7.2). Figure 7.2 reveals groundwaters in the
north slope are isotopically more depleted than those in the other slopes and,
groundwaters between 500 and 1000 m a.m.s.l. are isotopically depleted
compared with those at about 1500 m a.m.s.l. One reasonable explanation for
this is that the groundwaters of 500-1000 m a.m.s.l. are recharged from
precipitation at higher altitudes, thus reducing the D values of lower level
groundwaters to values below those of the 1500-m groundwaters.

Fig. 7.2 D vs. altitude diagram for groundwaters on the north and
other slopes of Mt. Fuji. Source areas of recharge to the
respective groundwaters were estimated based on the
recharge-water lines (Yasuhara et al., 1997).
4. The D values of groundwater samples from springs and wells were plotted
as a function of altitude (Fig. 7.2). Figure 7.2 reveals groundwaters in the
north slope are isotopically more depleted than those in the other slopes and,
groundwaters between 500 and 1000 m a.m.s.l. are isotopically depleted
compared with those at about 1500 m a.m.s.l. One reasonable explanation for
this is that the groundwaters of 500-1000 m a.m.s.l. are recharged from
precipitation at higher altitudes, thus reducing the D values of lower level
groundwaters to values below those of the 1500-m groundwaters.

113
5. The source areas of recharge to the respective springs and wells were
estimated with an aid of the recharge-water line (Fig. 7.2). Extrapolation
along a vertical line from a measured D value for a given sample would
intersect the recharge-water line at an altitude where recharge takes place. The
altitude corresponding to the D value of each groundwater sample ranges
between 1100 to 2000 m, 1250 to 2200 m, 1600 to 2250 m, and 1400-2700 m
for the south, east, west, and north slopes, respectively. The isotopically-
determined recharge areas are presented in Fig. 7.3, indicating those in the
north slope at considerably higher altitudes than the other slopes. This is
probably due to the distribution of pervious lava flows of younger age up to
high altitudes in the north slope.

Fig. 7.3 Isotopically-determined recharge areas for groundwaters in Mt.
Fuji (Yasuhara et al, 1995).
Chapter 7
114
6. There is a marked off-set (Fig. 7.1) in D between precipitation and
recharge-water lines at a given elevation for each of the slopes. ranges from
10 at 3000 m a.m.s.l. to 26 at 1000 m a.m.s.l. for the leeward north slope
and from 8 at 3000 m a.m.s.l. to 23 at 500 m a.m.s.l. for the windward
slopes. This difference in D probably results from isotopic enrichment caused
by evaporation during infiltration in recharge areas. Based on these values,
the altitude distribution of annual evaporation rate (% of annual precipitation),
E, on each slope can be calculated using the Rayleigh-type equation:

1 10
3
F
1
(7-1)

where F is the residual fraction of precipitation and is the equilibrium
hydrogen isotope fractionation factor. The evaporation rate, E, is obtained by:

E (1 F) 100 (7-2)

The equations such as Majoube (1971) and Kakiuchi and Matsuo (1979)
provide the equilibrium hydrogen isotope fractionation factor between liquid
and vapor phases at a given air temperature. Mean annual air temperature
necessary for the calculation of , is estimated by extrapolating the JMA
weather station data and others to the respective altitudes. As Mt. Fuji is close
to the Pacific Ocean and very humid, evaporation is considered to take place at
slow rate under a quasi-equilibrium condition. This assumption is verified by
the fact that on the D vs.
O diagram, groundwaters plot very close to the

local meteoric water line, having a slope of > 7.0. Therefore, the evaporation
rate calculated based on D from Eqs. (7-1) and (7-2), which takes into
account the equilibrium fractionation factor alone, is assumed to be
representative and reasonably accurate. The results are shown in Fig. 7.4,
indicating (1) the higher the elevation is, the lower the evaporation rate; (2)
evaporation from the leeward north slope is more than that from the windward
slopes due to a longer duration of sunshine and lower humidity on the north
slope.

115

Fig. 7.4 Isotopically-determined evaporation rate (% of annual
precipitation) from the leeward north and windward other
slopes of Mt. Fuji (Yasuhara et al., 1997).

7. Once the recharge altitudes and evaporation rates were obtained, the details
of groundwater flow and water balance for each of the slopes were worked out
by additional chemical, radioisotope, and field data.
The results of Mt. Fuji study are very suggestive. First, for a high
mountain, the altitude effects have to be determined for the respective slopes
by taking into account a predominant wind direction which produces heavy
rains. As was observed in Mt. Fuji, the so-called rain-shadowing effect is
comparable on a small scale with continental effect, and may tend to result in
different isotopic composition of both precipitation and groundwater between
one slope and the next. Similar phenomenon, more depleted isotopic values on
the leeward side of a mountain than windward side, was observed at the
Rocky Mountains in North America by Friedman and Smith (1970) and at the
Alps and Jura in Switzerland by Siegenthaler and Oeschger (1980).
Secondly, a recharge-water line should be used rather than a precipitation
line for an accurate estimation of recharge altitude. For areas such as Kilauea
volcano with little soil, very high infiltration rates, and rains of high intensity,
it is reasonable to assume precipitation isotopic composition is equivalent to
recharge isotopic composition (Scholl et al., 1996). In other places, however,
Chapter 7
116
evaporation from soil may tend to isotopically enrich recharge relative to
precipitation. As a result, two lines become not identical and a recharge-water
line is often located far above the precipitation line on an isotope-altitude
diagram (Fig. 7.1). Therefore, determining recharge altitude based on the
precipitation line would often result in underestimating the altitude of a source
area of recharge.
Thirdly, the characteristic trends imparted by evaporation can be useful
in understanding recharge processes, as well as determining recharge rates.
Infiltrating water in humid regions also has experienced great evaporative
enrichment. However, the observation that the slope of the D vs.
18
O
relationship for groundwaters is 7.0 or more (Yasuhara et al., 1997), very
close to that of the local meteoric water line, strongly suggest that evaporation
takes place slowly under a quasi-equilibrium condition. Thus, it causes little
to no non-equilibrium enrichment in the residual water. This is also the case in
other Japanese volcanoes with thick vegetation (e.g. Kazahaya and Yasuhara,
1994). To the contrary, in areas with less humidity, kinetic (non-equilibrium)
evaporation will become maximum. The overall fractionation for evaporation
is then the sum of the fractionation factor for equilibrium water-vapor
exchange and the kinetic factor, and the slope varies between about 3 and 5
depending on humidity. The fractional water loss from evaporation in low-
humidity areas, therefore, has to be calculated based on this overall
fractionation factor. For the details of the kinetic evaporation, the reader is
referred to Gonfiantini (1986) and Clark and Fritz (1997).

117

Fig. 7.5 Monthly mean
O values in precipitation and monthly mean

air temperatures for Swiss stations (Siegenthaler and
Oeschger, 1980).

Fig. 7.6 Dependence of monthly mean
O values of precipitation on
monthly precipitation amount. An example at Binza, Congo
(Dansgaard, 1964).
Chapter 7
118
In addition to the altitude effect, other effects also proved to be a
powerful tool for tracing groundwater. Figures 7.5 and 7.6 show the
dependence of the isotopic composition of precipitation on air temperature and
amount of rain, respectively. The annual temperature cycle is followed by the
corresponding changes of monthly mean
O values in precipitation,
reflecting a pronounced temperature effect of 0.35-0.5
O/C (Fig. 7.5).

The temperature effect is well seen in areas with seasonal variation in rains
during cold and warm seasons, and winter precipitations tend to be
isotopically depleted with respect to summer rains. An elegant example from
Congo for the amount effect is given in Fig. 7.6: greater monthly rain amounts
result in more negative
O values, suggesting an effect of -2.2
O/100
mm rain. Dansgaard (1964) reported a smaller amount effect (-1.6
O/100
mm rain) for the Wake Island in the Pacific Ocean.
These effects, in association with the degree of evaporative enrichment of
groundwaters, have been used to determine the season which is the most
responsible for infiltration and groundwater recharge. Winograd and Riggs
(1984) were able to discern groundwater recharge to the Spring Mountains in
southern Nevada that occurs primarily by winter precipitation, whereas
summer precipitation seems to be rarely involved in recharge. Ingraham et al.
(1991) concluded that both summer and winter precipitation are responsible
for recharging the groundwater in southern Nevada. However, for summer
precipitation, recharge may only be accomplished by larger precipitation
events of enriched isotopic composition and some of them 'short-circuit' the
perched water table. In northern Oman, Clark and Fritz (1997) succeeded in
tracing the source of groundwaters: isotopically depleted deep groundwaters
in fractured carbonate aquifers are dominated by recharge from winter rains
which occur under cooler conditions with greater intensity and duration;
whereas shallow alluvial groundwaters, which have experienced greater
evaporative enrichment, indicate recharge by summer rain under hot and dry
conditions.

7.1.2 Groundwater mixing

Unlike most goechemical tracers,
2
H and
18
O are inert and conservative
in mixing relationships. Therefore, stable isotopes can serve to quantify
groundwater mixing at the local to watershed scale where mixing between
groundwaters of different recharge origins, from different aquifers, and flow
119
systems, can take place. Mixing between two distinct groundwaters (end-
members) is quantified by simple linear algebra using D or
O. Figure 7.7,
for example, shows the fraction (X) of groundwater A in a mixture of two
groundwaters A (
A
) and B (
B
). The proportion of mixing for a given sample
in a two-component mixing system will then relate directly to its position on
the mixing line, according to:

sample
= X
A
+ (1-X)
B
(7-3)

An example of two-component groundwater mixing is given in Fig. 7.8. Two
mineral springs, the Hamei Zohar and Hamei Yesha springs, are seen to lie on
a fresh water-Dead Sea mixing line, indicating these springs are formed by
intermixing of Dead Sea water (brine) brought to the surface with the
emerging local fresh water recharged at the Judean Mountains (Gat et al.,
1969).

Fig. 7.7 Fractional mixing of two groundwaters quantified on the basis of their
isotopic composition, and it is shown as the fraction of groundwater A
in a mixture of A and B.
Chapter 7
120

Fig. 7.8 Isotopic composition of two mineral springs on the Dead Sea shores,
indicating these springs are formed by intermixing of Dead Sea brine
with local fresh water (Gat et al., 1969).

A three-component mixing system was identified by Kawanabe et al.
(1999) for groundwaters from the seepage caldera lake district in the
southernmost part of Japan. The evaporative enrichment in D and
18
O of the
Lake Ikeda water, that is the departure of the isotopic composition from the
meteoric water line, permits the recognition of the contribution of lake water
to the shallow aquifer and to the discharge of springs and rivers located
downgradient the lake. In their study, mixing between lake water, rain water,
and sea water was quantified based on the D vs.
18
O diagram (Fig. 7.9) and
18
O vs. Cl
-
diagram (Fig. 7.10).
indicating these springs are formed by intermixing of Dead Sea brine
with local fresh water (Gat et al., 1969).
121

Fig. 7.9 Plot of
18
O and D for waters around Lake Ikeda, a seepage
caldera lake in the southernmost part of Japan (Kawanabe
et al., 1999).

In Fig. 7.9, three end-members of recharge to the groundwater system are
isotopically distinct: (1) lake water; (2) rain water; and (3) sea water. The
isotopic composition of samples from the lake and also from many rivers, hot
springs, wells, and springs, are seen to lie on a straight line distinctly different
from the local meteoric water line. A regression carried out on these samples
results in a line with a slope of about 5.0, which is characteristic of open water
caldera lake in the southernmost part of Japan (Kawanabe
et al., 1999).
Chapter 7
122
bodies subjected to evaporation. A point for the rain water, which is a
potential source of recharge to the groundwater system, is marked in Fig. 7.9
on the extension of the line at the intersection with the local meteoric water
line. The values of -36 D and -6.0
18
O are considered to be
representative of the local rain water. The alignment of data points on this
lake water-rain water mixing line (LRL) is explained by simple mixing, in
varying proportions, of the isotopically depleted local rain water and enriched
lake water which leaks from Lake Ikeda. On the other hand, data points for
some rivers, wells, and hot springs do not align on the LRL (Fig. 7.9). They
exhibit a positive D shift of 2-3 and scatter between the LRL and the sea
water-rain water mixing line (SRL). This is indicative of contribution of sea
water to these waters. Figure 7.10 illustrates the variation of
18
O against the
Cl
-
concentration of samples which plot on the LRL or those of partial sea
water origin (Fig. 7.9). From Fig. 7.10, it is obvious that the Cl
-
concentration
is a result of mixing of lake water (Lake Ikeda; -3.0
18
O; 0.3 mmol l
-1
Cl
-
),
rain water (-6.0
18
O; 0.2 mmol l
-1
Cl
-
), and sea water (-0.1
18
O; 544
mmol l
-1
Cl
-
).
Based on Fig. 7.10, mixing proportion of each end-member is calculated
by applying a three-component mixing model, which is fundamentally in the
same manner as determined for a two-component mixing system. The
interpretation of the results (Fig. 7.11) suggests that groundwater regime has
considerable southerly and easterly leakage with less northerly leakage.
Southerly leakage is especially significant, that contributes to more than 70%
of the discharge of certain springs and rivers. Many of the wells and hot
springs also represent 7-100% lake water contribution.
To quantify groundwater mixing, numerous isotopic investigations have
been conducted in areas with various climates, hydraulic regimes, and
hydrogeological settings. Case studies including mixing of groundwater in a
dual porosity karst system and regional flow system, and mixing between
meteoric waters and brines are given in the literature (Kharaka and
Carothers,1986; Clark and Fritz, 1997).
123

Fig. 7.10 Plot of
18
O and Cl
-
concentration for waters in the Lake
Ikeda district (Kawanabe et al., 1999).

7.1.3 Palaeo-groundwaters

Palaeo-groundwaters (fossil groundwaters) are defined as groundwaters,
which have been recharged in the past by meteorological conditions that no
longer prevail. As they are now separated from the actively recharged flow
systems, these resources are finite and can not be replenished easily once they
are used up.
Ikeda district (Kawanabe et al., 1999).

Chapter 7
124

Fig. 7.11 Isotopically-determined mixing proportion of three end-members for
waters in the Lake Ikeda district (S: springs; R: rivers). The
results for wells and hot springs are not shown, but they represent
7-100% lake water contribution (Kawanabe et al., 1999).

The apparent link between local air temperature and isotopic composition
of both precipitation and groundwater (temperature effect in Chapter 7.1.1)
suggests the potential importance of
2
H and
18
O as palaeoclimatic indicators.
It is known that temperate latitude climates have experienced significant
changes in temperature since late Pleistocene time, whereas precipitation
variability has dominated low latitude palaeoclimate change. These climate
changes are manifested by a shift in isotopic composition of groundwaters on
the meteoric water line, and deuterium excess value (deuterium excess value
is as: d = D - 8
18
O), that is a departure of the isotopic composition from the
waters in the Lake Ikeda district (S: springs; R: rivers). The
results for wells and hot springs are not shown, but they represent
7-100% lake water contribution (Kawanabe et al., 1999).
oI bolh precipilalion and yroundaler |lemperalure eIIecl in 7.J.J)
125
present meteoric water line. Based on these isotopic signatures preserved in
palaeo-groundwaters, numerous studies carried out during the last three
decades were directed toward reconstruction of past climate conditions and
recharge processes.
In temperate regions, the dominant effect of climate change is reflected
in the position of meteoric water on the local meteoric water line. Figure
7.12A shows the isotopic depletion for Late Pleistocene palaeo-groundwaters
as compared to modern groundwaters for some parts of Europe. Palaeo-
groundwaters plot on the line essentially identical with the present meteoric
water line but are shifted toward negative values by ~ 18. If one applies a
temperature effect of 2.5 0.3 C
-1
for the continental European stations,
where monthly precipitation data is collected, depletion in D corresponds to
a decrease in the annual mean air temperature by ~ 7C (Rozanski, 1985).
Another interesting feature of Fig. 7.12A is that depletion in the isotopic
composition of palaeo-groundwaters is not accompanied by a reduced value of
deuterium excess, compared to the present-day conditions. Rozanski (1985)
concluded that this most likely indicates a constant relative humidity in the
source region that brings precipitation to Europe, and a relative constancy of
atmospheric circulation over Europe for past 35000 years. On the other hand,
Fritz (1983) and Seigel and Mandle (1984) cautioned that much of the
isotopically depleted Pleistocene groundwaters in the northeastern North
America might have originated from glacial meltwater and thus it should not
be interpreted in terms of local palaeoenvironments.
In Japan, depleted isotopic composition and little to no shift in deuterium
excess value were reported in palaeo-groundwaters at the foot of Mt.
Yatsugatake and the Tokyo Bay coast. Yasuhara and Kazahaya (1994)
concluded the Yatsugatake palaeo-groundwaters may have originated from
precipitation to the summit area under a climate condition 2-3C cooler than
modern annual temperature. Origins of the palaeo-groundwaters at Tokyo Bay
coast are still unclear (A. Marui, Geological Survey of Japan, written
communication, 2000).
Unlike the isotopic depletion as observed for temperate region palaeo-
groundwaters, the palaeoclimatic effect in arid regions is often manifested by
a displacement of the meteoric water line (Fig. 7.12B). In arid regions like the
North Africa and Middle East, palaeo-groundwaters, which are thought to
have been recharged in Pleistocene time under pluvial (humid) climates, are
characterized by low deuterium excess values as well as the depletion in
2
H
Chapter 7
126
and
18
O with respect to the modern waters. These palaeo-waters have
deuterium excess values of 5 or less, which are substantially lower value
than presently observed in meteoric waters of the regions. Sonntag et al.
(1979) attributed the shift in deuterium excess value to higher relative
humidity of the marine atmosphere by ~10% during the last glaciation.
Rozanski (1985) explained the low deuterium excess values as a sequence of
intense re-evaporation of rain water at the recharge areas. Additionally, many
alternative explanations have been given to the observations (e.g. Clark and
Fritz, 1997), but reasons for this shift and the apparent discrepancy between
the deuterium excess values in the European and North African palaeo-
groundwaters are still controversial.

Fig. 7.12
18
O vs. D diagram for palaeo-groundwaters (Pleistocene
groundwaters) in Europe (Fig. 7.12A) and in North Africa and
Middle East (Fig. 7.12B) compared with modern local meteoric
water and the global meteoric water line. From Clark and Fritz
(1997), who compiled data of Rozanski (1985) and others.
127
7.2 Groundwater dating with
3
H

Naturally occurring radioactive isotopes that exist in water in the
hydrologic cycle have been used to investigate groundwater system since early
1950's. One of such isotopes is tritium (
3
H), which is used to determine the
age of groundwater; i.e. the length of time it has been isolated and lost contact
with the atmosphere.

7.2.1 Natural and man-made
3
H

Tritium is a heavy isotope of hydrogen with a half-life of 12.4 years. The
concentration of tritium in water is expressed by tritium unit (TU). A tritium
unit is the equivalent of 1 tritium atom in the 10
18

atoms of hydrogen (
1
H).
The tritium in water in the hydrologic cycle has both natural and man-made
sources. Tritium is produced naturally in the upper atmosphere by interaction
of cosmic-ray-produced neutrons (n) with nitrogen (
14
N), producing
15
N,
which is radioactive and disintegrates into common carbon (
12
C) and tritium
(
3
H). Subsurface production could take place through the fission of
6
L, but it
is insignificant in terms of magnitude.
Tritium atoms are oxidized to water and mixed with precipitation, thus
enter to the groundwater. The natural tritium content in precipitation ranges
from 5 to 20 TU (Payne, 1972). Starting in 1953, however, the testing of
nuclear weapons added large amounts of man-made tritium to the atmosphere,
as a result increase in groundwater as well. They reached a peak in 1963, with
up to 10000 TU in a single month rain in the United States. This 1963 peak
became a marker used in many hydrological studies. A Soviet-American treaty
stopped surface nuclear bomb tests in 1963, and thereafter tritium
concentrations in precipitation decreased steadily. The man-made tritium
completely masked the natural tritium production, but the concentration of
tritium in precipitation is now largely back to natural, i.e., cosmogenic levels.
Tritium data obtained by the International Atomic Energy Agency
(IAEA) from a global sampling network enable us to estimate tritium versus
time trends for areas where there are no sampling stations or only short-term
records. Some patterns are seen in the global and seasonal distribution of
tritium concentrations in precipitation. At a given latitude, the concentration
of tritium in precipitation near the coast are lower than those inland because
of dilution from oceanic water vapor, which is low in tritium. Tritium values
are much higher in the northern hemisphere, where more bombs tests took
Chapter 7
128
place than south. A spring-summer peak and winter low were observed in each
year, reflecting the fact that tritium generated in higher parts of the
atmosphere leaked in the spring and summer into the lower parts.

7.2.2
3
H as a short-term age indicator

Groundwater dating based on tritium uses the fact that the initial
concentration A
0
(expressed in TU) in recharging groundwater decreases with
time according to the decay equation:
A(t) = A
0
e
-t

(7-4)

where A(t) is the tritium concentration measured in a sample after decay over
time t. The decay term

is equal to ln2 divided by the half-life. This
equation can be rearranged, and upon substitution of T = 12.4 years yield:

t = -17.93 ln (A(t) / A
0
)
(7-5)

For example if A
0
= 10 TU, which is representative of pre-bomb and present
tritium concentrations in precipitation, Eq. (7-5) gives the decay series:

years: 0 10 20 30 40 50 60
TU : 10 5.7 3.3 1.9 1.1 0.6 0.4

Thus, due to its relatively short half-life, the useful range for groundwater
dating with tritium is less than 40-50 years when the enriched method
(detection limit = 0.8 TU) are used for the analyses.
Under an ideal situation, the initial tritium concentration is well known
and no processes other than decay can change the concentration as the water
moves through an aquifer. Such a situation, however, is hardly ever found in
nature. Tritium concentration in precipitation is known to show spatial,
seasonal, and intra annual variations. Moreover, complicated mixing often
occurs in an aquifer and the mode and extent of mixing of each year's recharge
with that of previous years' recharge is difficult to know. Mixing with another
water bodies are also plausible. Hence, a single groundwater age determined
from Eq. (7-5) often has no meaning. However, semiquantitative dating is still
possible and informative. Tritium is often used in a semiquantitative manner
0 10 20 30 40 50 60
129
to date groundwater in the sense that water with zero tritium (in practice < 0.8
TU) is dated prior to 1953; water with little, but measurable tritium (0.8-1 TU)
seems to be a mixture of pre-1953 (submodern or palaeo-groundwater) and
post-1953 water; water with a concentration greater than some 10 TU is of a
post-1953 age and a significantly high concentration (> ~ 30 TU) indicates
recharge during the 1960s.
For the last three decades, attempts have been made to establish
quantitative approaches to dating groundwaters with tritium, that is the
introduction of lumped-parameter models. Recall again that each water
molecule in a groundwater sample has its individual history, and a single
groundwater age does not strictly exist. Any given groundwater is a mixture of
waters with a distribution of ages, and it is generally impossible a priori to
know that distribution. Consequently, only "model ages" based on
hypothetical age distributions can be calculated (Loosli et al., 1991). Models
for two extreme distributions are in common use. In the piston flow model
(PFM), it is assumed that there are no flow lines of different velocities and
diffusion, dispersion, and mixing along flow path are negligible. In other
words, it assumes unmixed flow in a closed system, as in a pipe, so that all
water at a give location has virtually the same age and the age of water in a
given reservoir (aquifer) varies with space. The problem with this approach is
its simplicity, not representative of natural systems. The exponential model
(EM) assumes that the age distribution is described by an exponential law so
that younger water is present more frequently than older water. This model is
mathematically equivalent to the well known model of good mixing which is
successfully applied to some lakes. A mean residence time can be calculated
from the EM. A more realistic model combines the properties of the models
discussed above and is referred to as the exponential-piston model (EPM). In
the EPM, it is assumed that the aquifer consists of two parts in line, one with
an exponential distribution of residence times, and another with a distribution
which may be approximated by the PFM. Other models also exist (e.g. Zuber,
1986), and usually it is very difficult to decide which model is closest to
reality. The reader is referred to Chapter 8 for the case studies on tritium-
based groundwater dating.
Chapter 7
130
References

Clark, I. and P. Fritz, Environmental Isotopes in Hydrogeology, Lewis, 328p,
1997.
Dansgaard, W., Stable isotopes in precipitation. Tellus, 16, 436-468, 1964.
Friedman, I. and G. I. Smith, Deuterium content of snow cores from Sierra
Nevada area. Science, 169, 467-470, 1970.
Fritz, P., Paleoclimatic studies using freshwater deposits and fossil
groundwater in central and northern Canada. In: Paleoclimates and
Paleowaters: A Collection of Environmental Isotope Studies, IAEA, 157-
166, 1983.
Gat, J.R., Mazor, E. and Y. Tzur, The stable isotope composition of mineral
waters in the Jordan Rift Valley. J. Hydrol., 7, 334-352, 1969.
Gonfiantini, R., Environmental isotopes in lake studies. In: Handbook of
Environmental Isotope Geochemistry (Volume 2), P. Fritz and J.Ch.
Fontes (eds.), Elsevier, 113-168, 1986.
Ingraham, N.L., Lyles, B.F., Jacobson, R.L. and Hess, J.W., Stable isotopic
study of precipitation and spring discharge in southern Nevada. J. Hydrol.,
125, 243-258, 1991.
Kakiuchi, M. and Matsuo, S., Direct measurements of D/H and
18
O/
16
O
fractionation factors between vapor and liquid water in the temperature
range from 10 to 40 C. Geochem. J., 13, 307-311, 1979.
Kawanabe, Y., Yasuhara, M., Marui, A., Kohno, T. and Satoh, Y., An isotopic
study on the groundwater regime of a seepage caldera lake district,
southern Japan. In: Integrated Methods in Catchment Hydrology, IAHS
Publ. no. 258, 183-192, 1999.
Kazahaya, K. and Yasuhara, M., A hydrogen isotopic study of spring waters in
Mt. Yatsugatake, Japan: Application to groundwater recharge and flow
processes. Hydrology, 24, 107-119, 1994.
Kharaka, Y.K. and Carothers, W.W., Oxygen and hydrogen isotope
geochemistry of deep basin brines. In: Handbook of Environmental Isotope
Geochemistry (Volume 2), P. Fritz and J.Ch. Fontes (eds.), Elsevier, 305-
360, 1986.
Loosli, H.H., Lehmann, B.E. and Dapen, G., Dating by radionuclides. In:
Applied Isotope Hydrology -A Case Study in Northern Switzerland, F.J.
Pearson Jr., W. Balderer, H.H. Loosi, B.E. Lehmann, A. Matter, Tj. Peters,
H. Schmassmann and A. Gautschi, Elsevier, 153-174, 1991.
131
Majoube, M., Fractionnement en oxygene 18 et en deuterium entre l'eau et sa
vapeur. J. Chim. Phys., 10, 1423-1436, 1971.
Mazor, E., Chemical and Isotopic Groundwater Hydrology -The Applied
Approach (2nd edition), Dekker, 413p, 1997.
Payne, B.R., Isotope hydrology, Adv. Hydrosci., 8, 95-138, 1972.
Payne, B.R. and Yurtsever, Y., Environmental isotopes as a hydrogeological
tool in Nicaragua. In: Isotope Techniques in Groundwater Hydrology 1974
(Volume 1), IAEA, 193-202, 1974.
Rozanski, K., Deuterium and oxygen-18 in European groundwaters -Links to
atmospheric circulation in the past. Chem. Geol. (Isotope Geoscience
Section), 52, 349-363, 1985.
Scholl, M.A., Ingebritsen, S.E., Janik, C.J. and Kauahikaua, J.P., Use of
precipitation and groundwater isotopes to interpret regional hydrology on a
tropical volcanic island: Kilauea volcano area, Hawaii. Water Resour. Res.,
32, 3525-3537, 1996.
Seigel, D.I. and Mandle, R.J., Isotopic evidence for glacial meltwater recharge
to the Cambrian-Ordovician aquifer, north-central United States. Quat.
Res., 22, 328-335, 1984.
Siegenthaler, U. and Oeschger, H., Correlation of
18
O in precipitation with
temperature and altitude. Nature, 285, 314-317, 1980.
Sonntag, C., Klitzsch, E., Lohnert, E.P., El-Shazly, E.M., Munnich, K.O.,
Junghans, Ch., Thorweihe, U., Weistroffer, K. and Swailem, F.M.,
Paleoclimatic information from deuterium and oxygen-18 in carbon-14
dated north Saharian groundwaters: Groundwater formation in the past. In:
Isotope Hydrology 1978 (Volume 2), IAEA, 569-581, 1979.
Winograd, I.J. and Riggs, A.C., Recharge to the Spring Mountains, Nevada:
Isotopic evidence. Geol. Soc. Am., Abstr. Prog., 16, 698, 1984.
Yasuhara, M. and Kazahaya, K., A geochemical study of deep groundwater in
Mt. Yatsugatake. Hydrology, 24, 121-132, 1994.
Yasuhara, M., Marui, A., Kazahaya, K., Suzuki, Y. and Takayama, S., An
isotopic study toward the protection of groundwater resources in Mt. Fuji,
Japan. In: Solutions '95 (Proc. IAH XXVI Int. Cong.), 1224-1229, 1995.
Yasuhara, M., Marui, A. and Kazahaya, K., Stable isotopic composition of
groundwater from Mt. Yatsugatake and Mt. Fuji, Japan. In:
Hydrochemistry, IAHS Publ. no. 244, 335-344, 1997.
Zuber, A., Mathematical models for the interpretation of environmental
radioisotopes in groundwater systems. In: Handbook of Environmental
Chapter 7
132
Isotope Geochemistry (Volume 2), P. Fritz and J. Ch. Fontes (eds.),
Elsevier, 1-59, 1986.
Use of environmental isotope tracers to reveal groundwater flow system
133
Chapter 8

Use of environmental isotope tracers to reveal groundwater flow
system

8.1 Introduction

The environmental radio isotopes like tritium and radio carbon work as an
age tracer of the groundwater. While the environmental stable isotopes of oxygen
and hydrogen in the water tells us the origin of the water and work as a space
tracer. The combination of these environmental isotopes were widely used in the
hydrological field studies during last 30 to 40 years and had made great success to
reveal the hydrological process including groundwater flow.
In this chapter, typical examples of environmental isotopes used to reveal the
groundwater flow system in a particular field, which is composed not only by the
unconsolidated alluvial or diluvial aquifer but also by the fractured bedrock
aquifer, will be introduced to show the effective use of the environmental isotopes.

8.2 Tracing of groundwater flow in the bedrock by means of environmental
tritium

In the bedrock, many cracks and fissures originates from crust diastrophism.
The groundwater is stored in these cracks and fissures and moves downward
through them by gravity. Cracks and fissures in the bedrock have very different
shapes such as tubular or plane-type, and they cross, expand and connect each
other making a very complex structure. Nevertheless from a macroscopic point of
view the network of these cracks and fissures compose the storage zone or
pervious layer. In case many irregular and non-homogeneous fissures exist in the
bedrock and made a network of fissures, then it may be reasonable to consider this
bedrock hydraulically homogeneous.
Hubbert (1940) solved the groundwater flow analytically in isotropy and
homogeneous media. After that, Toth (1962) and Freeze and his co-workers (1967) homoyeneous media AIler lhal, Jolh |J962) and Ireeze and
\ilherspoon |J967)
Chapter 8
134
tried to estimate the flow in more complex pervious layer using computer
simulations. However, the actual measurement of the groundwater flow was
observed in most case in an alluvium deposit, and was very rare in bedrock.
Recently the research has been conducted in USA, Canada, Sweden, and some
NATO countries on the groundwater in bedrock related to the geological disposal
of high level nuclear waste and they are expected to reveal the groundwater flow
observation in bedrock.
This paper introduces the two examples of the groundwater observation
within bedrock in Japan traced by the environmental isotopes. The precise results
have already been published in different papers (Shimada et al. 1980, Shimada and
Ishii 1986).

8.2.1 Hydrological case study of a small granite island

(a) Description of the island
The investigated area is a small granite island located in Seto Inland Sea,
Japan, whose dimensions are about 1km from east to west, 3km from south to
north, and 154 m above sea level at the highest point. As the result of geological
survey, this island mainly consisted of "Hiroshima granitic rocks" of Cretaceous
age intruded by porphyrite and aplite. The fractured zones strikes almost north to
south and lay in a parallel arrangement as shown in Fig. 8.1. Totally 13 boreholes
were drilled as shown in Fig. 8.1, the core observation and many other kinds of
geological and hydrological logging has executed within these boreholes.

(b) Potential distribution of groundwater
The flow of the groundwater can be understood by describing the potential
distribution. In this study, the groundwater pressure in the boreholes was measured
by the double-packered apparatus. The measurements were done at every 5 m
intervals from the groundwater level to the bottom in each borehole. By using
those measured data, the groundwater potential distributions of this island, along
the cross section of x-y in Fig. 8.1, were drawn as Fig. 8.2.
1apan, \hose dimensions are aboul J km Irom easl lo esl, 3 km Irom soulh lo
135

Fig. 8.1 Geological map of the island and location of drilled boreholes.

Fig. 8.2 Potential distribution of the bedrock groundwater in the island.

Some high-pressure zones near the central parts of the island can be
explained by considering the three dimensional groundwater flows which moves
along the fragile part, such as fractured zone, and vertical to the x-y cross section.
From this figure, it can be seen that the groundwater flows within the bedrock of
Chapter 8
136
this island from the central peak to down the marginal coastal part of the island.
This fact supports the continuous flow of the groundwater in the bedrock aquifer.

(c) Groundwater movement traced by the environmental tritium
The tritium concentrations in precipitation of Japan have been measured
continuously at Tokyo from 1960s (IAEA, 1969, 1970, 1971, 1973, 1975). The
lack of data before 1960 was recovered by the estimation from the data of Ottawa
(Shimada 1976). The data before 1950 was estimated from the fluctuation of sun
spot number. Arranging all of these data, the fluctuation of the tritium
concentration in precipitation of Tokyo is shown in Fig. 8.3 In this figure, the
decayed concentration are adjusted to the groundwater sampling date (Nov.1979),
is shown as a solid line.
The Bomb tritium front (above 1 T.U.) is clearly shown on the tritium
distribution in Fig. 8.4, which could be effectively used to separate the
groundwater age distribution of this island. This figure also shows more clear
existence of the bedrock groundwater flow than the flow system estimated from
the previous potential distribution. The apparent flow velocities of the bedrock
groundwater of this island are about 1.7 ~ 4.1 x 10
-5
cm/sec determined by this
figure, which shows close agreement between the results of in-situ permeability
measurement at each boreholes.

Fig. 8.3 Tritium concentration in precipitation at Tokyo.
.
deca,ed concenlralion are ad|usled lo lhe yroundaler sampIiny dale |ôV. J979),

Fig. 8.4 Distribution of the Tritium concentration in the bedrock groundwater of
the island.

8.2.2 Groundwater flow around the crystalline bedrock tunnel

(a) Description of the study area
The bedrock groundwater is mostly existed in fractures and should be moved
by gravity. The construction of the tunnel into this bedrock must induce a drainage
effect and the bedrock groundwater around a tunnel would be moved to drain.
During a tunnel construction, the seepage groundwater into a tunnel was sampled
for the water chemistry and environmental isotope analysis to reveal the change of
the groundwater regime around a tunnel before and after the tunnel construction.
The study area is a tunnel construction site of Mt. Tsukuba region in central
part of Japan. The tunnel was constructed from August 1981 to May 1985. During
the construction period, the seepage water along the tunnel was periodically
sampled in low-water and high-water seasons (July, 1982, April and August 1983,
February and August 1984). Six surface water samples around the tunnel
(T-02~T-07),and finally fifteen seepage water samples along the tunnel
(T-01,T-08~T-22) were collected to analyze.

(b) Conditions of water chemistry in groundwater
For each water sample, the water chemistry (Na
+
, K
+
, Ca
++
, Mg
++
,
Cl
-
,SO
4
--
,HCO
3
-
,SiO
2
) and the environmental isotopes (
3
H,D,
18
O,
14
C) were
measured. Figure 8.5 shows the time series change of water chemistry on a Piper
137
the island.
|J0J,J08 J22) ere coIIecled lo anaI,ze.
Chapter 8
138
diagram for the six continuously sampled seepage points in the tunnel. Soon after
the excavation, T-14 and T-17 shows sodium-bicarbonate type, while T-12, 13, 18
and 20 show the calcium-bicarbonate type composition. Except for T-17 and T-20,
it is clearly shown that after the excavation, the composition of water chemistry in
the seepage groundwater has changed from sodium-bicarbonate type, which
represents a deep confined groundwater, to calcium-bicarbonate type that
represents a shallow unconfined groundwater.

Fig. 8.5 Change of the water chemistry on the pipers plot in the seepage
groundwater into the tunnel during tunnel construction. groundwater into the tunnel during tunnel construction.
139

(c) Tritium concentrations in groundwater
The time series variations of tritium concentration in the previous
continuously sampled six seepage groundwater are shown in Fig. 8.6 The
concentration of the surface water is also shown in the figures which are averaged
concentration in the surface river samples. This figure shows decreasing tendency
with reflecting the long term decrease after the atmospheric nuclear weapon test
peak in 1965. On the contrary, the seepage bedrock groundwater into the tunnel
shows a distinct concentration increase after the tunnel excavation. The increase in
concentration is almost certainly due to the contribution of the recent young
surface groundwater.

Fig. 8.6 Change of the tritium concentration in the seepage groundwater into the
tunnel during tunnel construction.
.
tunnel during tunnel construction.

Fig. 8.7 Change of the mixing ratio of the surface origin groundwater in the
seepage groundwater during tunnel construction.

seepage groundwater during tunnel construction.

Chapter 8
140
It is possible to consider the simple mixing model for the seepage
groundwater. The concentration of the seepage groundwater (C) can be explained
by the mixture between old groundwater in the bedrock (C
o
) and the young surface
groundwater (C
y
);
C = (1-) C
o
+ C
y

where is mixing ratio. In this case, we consider the concentration of seepage
bedrock groundwater, sampled soon after the excavation as C
o
and the mean
concentration of the surface river water during the study period as C
y
. It is then
possible to calculate the fraction of the surface water in the seepage bedrock
groundwater from the above equation.
Figure 8.7 shows the time series variation of this ratio () after the excavation.
This figure shows that the displacement of old groundwater stabilizes at the
composition of 80 % young surface groundwater and 20 % old groundwater within
one or two years.

141
(d) Estimation of the groundwater flow around the tunnel
Before the tunnel construction, the groundwater flow was estimated to be
flowing through the relatively low permeability fractures in the bedrock aquifer (2
x 10
-6
cm/sec) as shown in Fig. 8.8(a). The excavation of the tunnel has influenced
the bedrock groundwater flow regime and induced the drainage flow as shown in
Fig. 8.8(b). This fact is supported by the time series change of the water chemistry
and also by the environmental isotope concentration change in the seepage
bedrock groundwater.
The relatively young surface groundwater with much Ca
++
, HCO
3
-
, and SiO
2

is seeping into the tunnel and in displacing the old bedrock groundwater. In this
study area, environmental tritium data shows that the displacement of old waters
are stabilized at a composition with 80 % of young surface groundwater and 20 %
of old groundwater within one to two years. In case it takes two years for these
young surface groundwater to penetrate through the fractures in the bedrock, the
traveling velocity of these groundwater should be ranged between 30 to 60 cm/day
which is equivalent to the permeability of 3 7 x 10
-6
cm/sec. This figure is
reasonable if we consider the effective porosity and the permeability of the
bedrock, and the depth of the tunnel from the ground surface.
It has been cleared by this study that the artificial underground facilities
induce very large perturbation into the relatively slow moving groundwater regime
in the bedrock. However, this artificially induced movement is still within Darcian
flow domain. It is because the results of the numerical simulations for porous
media type groundwater, with this particular boundary conditions, showed good
agreement with the estimated groundwater flow from the observation results of
water chemistries and environmental tritium.

Fig. 8.8 Conceptual image of the bedrock groundwater flow around a tunnel
before and after the tunnel construction.

8.3 Groundwater flow in alluvial and diluvial aquifers revealed by
environmental isotopes

8.3.1 Recharge origin of the groundwater in Kurobe alluvial fan

(a) Description of the Kurobe alluvial fan
The Kurobe alluvial fan is a typical seaside alluvial fan in the Japan sea side
before and after the tunnel construction.

Chapter 8
142
143
of the main Honshu Island, Japan, with relatively steep topographical gradient
(1%) and mainly composed by the alluvial gravel and sand of Kurobe River. The
hydraulic conductivity of these sand and gravel unconfined shallow aquifer is 0.5
to 1.0 x 10
-3
cm/sec. Deep confined aquifer covered by the 20 to 100m thickness
clay layer also exists near river mouth area which produces artesian flowing wells
along the sea shore. Most part of the fan is exclusively used for the rice paddies
where irrigation water from the Kurobe River is introduced during mid April until
early September.
In 1989 and 1990, groundwater table in the fan was observed using about 100
existing dug wells including the groundwater observation wells, and is shown in
Fig. 8.9 The shapes of the contour curves are almost parallel to the topographical
surface. Near the Kurobe river, convex shape contour has made by the
groundwater ridge along the river, where the Kurobe river water recharges the fan
groundwater. The seasonal fluctuation of the groundwater level shows high in May,
the irrigation season, and low in November, the relatively dry season in a year.

Fig. 8.9 Contour map of the groundwater table of Kurobe alluvial fan in Nov.
1989 and May and Aug. 1990.

1989 and May and Aug. 1990.
lo J0 x J0 cm/sec eep conIined aquiIer coVered b, lhe 20 lo J00 m
l h i c k n e s s

Fig. 8.10 The stable isotope composition of groundwater and river water of the
Kurobe fan. Kurobe fan.
Chapter 8
144
(b) Stable isotopes in the groundwater
It is well known that the stable isotope ratios in precipitation are mostly
affected by the temperature condition to produce the rain drops. Thus there exist
seasonal, latitudinal, and altitude changes in the stable isotopic composition in
precipitation. The altitude effect, the more depleted ratios obtained at higher
altitudes, is of particular useful in hydrological applications.
32 groundwater samples were collected including 21 dug wells and artesian
springs, 11 observation wells, and 3 river waters (Kurobe, Ogawa, and Funakawa
rivers) from all over the Kurobe alluvial fan. The deep groundwater samples (30 to
150 m below land surface) were taken from the observation wells. The results are
shown on the diagram in Fig. 8.10. In this figure the precipitation sampled at
Toyama city (about 30 km west to Kurobe) are also shown by open circles, whose
weighted mean is 54 for D and 9.4 for
18
O, respectively. The ratio of
the Kurobe river water shows most depleted value, 85 for D and 13.0 for
18
O, respectively, which are caused by the relatively high altitude of the river
catchments area (about 1600 m a.m.s.l.). The stale isotope ratio in the Kurobe fan
groundwater distributes between local precipitation and Kurobe river water, which
means that there exist two main recharge origins for the Kurobe fan groundwater;
local precipitation and Kurobe river water.

145
(c) The distribution of the stable isotopes in the alluvial fan
The
18
O distribution of the groundwater in the Kurobe alluvial fan is shown
in Fig. 8.11. It shows clear influence of the recharge from the Kurobe River. The
averaged value of the local precipitation shows relatively enriched values (C
p
=
9.4 for
18
O), whereas the Kurobe river water was most depleted (C
R
=
13.0 for
18
O). Thus the isotopic composition of the fan groundwater (C
G
)
could be explained by the mixture of the local precipitation and the Kurobe river
water, and is expressed by the following equation.
C
R

+ ( 1 - C
p
= C
G
where is the mixing ratio of the Kurobe river water. By this equation, the
recharge by the river water could be explained quantitatively; the isotopic content
in the groundwater (C
G
) with 12.0 for
18
O means 77 % contribution of
Kurobe river water, while C
G
with 11.0 for
18
O means 47 % contribution of
Kurobe river water. In Fig. 8.11, there are no clear anomalies between shallow
unconfined groundwater and deep confined groundwater for their isotopic content
distribution. The groundwater recharge origin is mostly affected by the distance
from the river and is identical to both unconfined and confined groundwater in the
alluvial fan. The more precise considerations have already published by Shimada
et al. (1993).

Fig. 8.11 The
18
O content distribution of the groundwater in the Kurobe fan.
Chapter 8
146
8.3.2 The residence time analysis of an unconfined groundwater in the
Musashino upland

(a) Description of the study area
Musashino upland, developing western part of the city of Tokyo, is composed
of sand and gravel layer covered by thick volcanic ash layer of late Pleistocene age
which is called Kanto loam. This upland consists of three terraced surfaces which
originate in the alluvial fan of old Tama river. The thickness of the Kanto loam
formation differs from terrace to terrace and the thickest deposits occur on the
upper surface named Musashino Terrace, which has a loam layer about 10 m thick.
The second thick is the middle terrace surface named Tachikawa Terrace with
about 5 m thick of loam. Under these loam layer, Quaternary sand and gravel layer
of approximately 3 to 10 m thick, which is the main unconfined groundwater
aquifer of these terraced uplands, overlying the Tertiary sedimentary bedrock.
Each terrace forms a separate unconfined groundwater table flowing toward east.
The hydraulic conductivity of the aquifer is about 1 x 10
-1
to 10
-2
cm/sec.

(b) Tritium concentration in the groundwater
In 1991 and 1992 groundwater sampling for tritium analysis was done for the
unconfined aquifer of Musashino and Tachikawa terrace (Fig. 8.12). There are not
much concentration differences for the spatial distribution but there exist clear
concentration difference between terraces as shown in Fig. 8.13. The piston type
downward movement of soil water recharging through the Kanto loam layer has
been confirmed by Shimada (1988). If the thickness of the penetrating loam layer
is different, the tritium concentration at the bottom of the loam layer must be
different; the thicker loam has older precipitation recharge with relatively high
tritium content. In such case, the downward velocity of the soil water is 1.3 1.4
m/y, the penetration time through the loam layer will be 5 years for Musashino
terrace with 5 to 9 m thick loam, while it will be 2.5 years for Tachikawa terrace
with 2 to 5 m thick loam.

147

Fig. 8.12 Location of sampling wells in Musashino and Tachikawa terraces.

Fig. 8.13 Difference of tritium concentration in the unconfined groundwater
between Musashino and Tachikawa terraces. between Musashino and Tachikawa terraces.
Chapter 8
148
(c) Residence time analysis by well mixing model using tritium concentration
In case of unconfined groundwater aquifer of the terraced sand and gravel
layer, because of the relatively high hydraulic conductivity and the horizontally
wide recharge through the covered loam layer, relatively easy mixing of the
recharging water and the groundwater body has occurred within the aquifer. In this
case, it is possible to apply the following well mixing model based on the tritium
balance.

(CV) / t = C
in
R C
o
Q (CV)

where, C : average tritium content in the aquifer
C
in
: tritium content in the inflow water to the aquifer system
C
o
: tritium content in the outflow water from the aquifer system
V : storage volume of the aquifer system
R : inflow volume to the aquifer system
Q : outflow volume from the aquifer system
: decay constant of tritium
If we consider the steady state condition in the system;
V / t = 0 and R = Q

and at instantaneous mixing of water in the aquifer, C
o
= C
above equation will become as follows.

d C
0
(t) / d t = -( + /T )C
0
(t) + /TC
in
(t)

where, T is the residence time in the aquifer system, which can be expressed by
V/R or V/Q.
In the present study, C
in
(t) is not the tritium concentration in the precipitation but
that in the bottom soil water in the Kanto loam layer that recharge the unconfined
gravel aquifer. This can be shown as follows ;

C
in
(t) = C
R
(t-T
P
)exp(-T
P
)

| )
\/R or \/Q. In lhe presenl slud,, C |l) is nol lhe lriliurm concenlralion
in lhe precipilalion bul lhal in lhe bollom soiI aler in lhe !anlo Ioam
Ia,er lhal recharye lhe unconIined yraVeI aquiIer. Jhis can be shon
as IoIIos,

149
Where, C
R
(t) is the tritium concentration in precipitation and T
P
is the penetrating
time to flow through the Kanto loam layer, which is 5 years for Musashino terrace
and 2.5 years for Tachikawa terrace, respectively.
Figure 8.14 shows the relationship between the tritium concentration in the
groundwater, as of the time of sampling on Aug. 1992, and the residence time
estimated from the well mixing model for Tachikawa and Mushashino terrace. The
longer residence time has the higher tritium content which was much influenced
by the old high tritium content of rain water. By this figure, the averaged tritium
concentrations both for Musashino and Tachikawa terrace groundwater, 7.1 T.U.
and 4.9 T.U., coincide with the residence time of about 6.5 years and 5 years,
respectively. Figure 8.15 shows the temporal variation of tritium concentration in
the groundwater with the above estimated residence time for both terrace
groundwater bodies estimated by the well mixing model. In case of Musashino
terrace groundwater, the previous three tritium measurements by the different
authors perfectly matched on the estimated tritium output function curve, which is
the good validation for the estimated model (Shimada et al, 1994).

Fig. 8.14 The relationship between the tritium concentration in the groundwater as
of the time of sampling, Aug. 1992, and the residence time estimated
from the well mixing model.
of the time of sampling, Aug. 1992, and the residence time estimated
from the well mixing model.
Chapter 8
150

Fig. 8.15 The temporal variation of tritium concentration in the groundwater
estimated by the well mixing model.

References

Freeze, R.A. and Witherspoon, P.A., Theoretical analysis of regional groundwater
flow 3, Quantitative interpretation, Water Resour. Res., 4, 581-590, 1967.
Hubbert, M.K., The theory of groundwater motion, Jour. Geol., 48, 785-944. 1940.
IAEA, ed (1969,1970,1971,1973,1975), Environmental isotope data Nos. 1-5:
World survey of isotope concentration in precipitation, Tech. Rep. Ser.
Shimada, J., Momota, H. and Ono, Y., Role of groundwater in the bedrock for
underground oil storage, A hydrological case study of small granite island.
Subsurface Space, Proc. of the Rock Store 80 Symp. 393-400, 1980.
Shimada, J. and Ishii, T., The influence on water chemistry in the crystalline
bedrock groundwater by Tsukuba tunnel construction, Proc. of 8
th
Geotech.
and Geohydr. Aspects of waste management, USA, 467-476, 1986.
151
Shimada, J., The mechanism of unsaturated flow through a volcanic ash layer
under humid climatic conditions, Hydrol. Processes. 2, 43-59, 1988.
Shimada, J., Kayane, I., Shimano, Y., and Taniguchi, M., Use of several
environmental tracers to detect the surface-subsurface water interaction in an
alluvial fan, Tracers in Hydrology, Proc. of IAHS Yokohama Symp. IAHS publ.
No.215, 263-274, 1993.
Shimada, J., Dapaah-Siakwan, S. and Yoshihara, M., Groundwater flow and
recharge characteristics of Musashino and Tachikawa terrace groundwater
revealed by environmental tritium. in Study on surface and subsurface water
interaction in the Tama river basin, Tokyo, Japan, ed. By Kayane, I. for Tokyu
foundation. 124-147, 1994. (in Japanese)
Toth, J.A., A theory of groundwater motion in small drainage basin in central
Alberta, Canada, Jour. Geol. Res., 67, 4375-4387, 1962.

Water in Arid Region
153
Chapter 9


9.1 Introduction

Arid region occupies about one third of the terrestrial area of the Earth.
Most part of this vast area is barren and left for human challenge to reclaim it
for their habitat.
The focal point in the development of arid region is apparently the
availability of water, in particular, freshwater. With the aid of contemporary
science and technology, freshwater resources have been searched for
vigorously, and the efforts seem to continue further in the future.
Hydrology on the arid region advanced noticeably in the later half of the
20th century, when mass-spectrometry started producing massive analytical
results on the stable isotopes of natural water, deuterium (D) and
18
O. During
this period, geochemists reported unique climate-related properties of the
mass-ratios, i.e.,
18
O/
16
O and D/H, of natural water. The results were so
remarkable that these environmental isotopes were regarded as natural tracers.
These results stimulated strong scientific interest among the hydrologists on
the arid region. Later on, hydrological science, intensively focused on the
environmental isotopes, began to be called Isotope Hydrology.
Isotope hydrology on the arid region is still in progress. It is extending its
applicability to the researches required in the frontiers where human activities
are intensified in recent years.

9.2 Arid Region: Global Distribution and Cause

Arid regions are distributed on our planet almost symmetrically to the
Equator. The distribution extends in zones from subtropical to mid-latitudes.
However, when examined geographically, they are categorized into three
groups: Inland arid region, coastal arid region and wind-shade arid region.
Among these groups inland arid region is the most extensive.
Water in arid region

Chapter 9
154
In the global sense, the general atmospheric circulation model can explain
the cause of arid environment. In this model, a large zonal circulation (a
meridional circulation) prevails in each hemisphere close to the equator,
driven by the thermal convection, called Intertropical Convergence Zone
(ITCZ). At the farther periphery from the equator, the circulation generates air
subsidance zones, and arid regions are caused there by the anti-cyclonic
system at the surface.
However, other effects, such as oceanic ones along the coasts washed off
by the cold current, and orographical ones on the leeward of shadowing
mountains, superimpose on the aridity.

9.3 Precipitation in the Arid Region

Meteoric water precipitates only when liquid or solid is separated from
the atmospheric water vapour. Nucleation is required for the atmosphere to
precede phase separation. Heterogeneous nucleation is prevalent, in which
exotic particulate works as nucleus in water vapour condensation.
Homogeneous nucleation, a process in a pure and homogeneous material, is
not easily achieved at the prescribed point of phase transition. In case of ice
nucleation in a condensed water droplet, it starts spontaneously only at the
very low temperature of 41 C. Instead in the proper cooling process, the
atmosphere first proceeds to super-cooling or super-saturation, then starts
nucleating at certain temperature, called an activation temperature, before
reaching the point of homogeneous nucleation.
In the precipitation process, raindrops and snowflakes grow as a result of
congregation and competition of minute super-cooled or frozen cloud droplets.
Frozen droplets exploit supercooled ones by the difference of saturation
vapour pressure, and accelerate the precipitation.
Two kinds of nucleation aerosol are known in the above processes; they
are sea salt particles and ice nuclei. Sea salt particles have oceanic origin and
ice nuclei are mainly of terrestrial and derived from weathered material.
Consequently, there are differences in the aerosols in the air mass according to
the transport trajectory; maritime or continental. On the Eastern Mediterranean
Coast, air masses are observed to carry different airsols depending on the
advection route, as presented in Fig. 9.1. When the maritime westerly blows,
sea salt particles are counted remarkably, but they are replaced with ice nuclei
when the wind shifts to the easterly, the continental one. In arid region, air

155
mass tends to be more continental due to the rich weathered material as dry
dust.
In the continental air mass, once the anti-cyclonic system is broken, the
ice nucleus effect enhances precipitation and strengthens convection.
Consequently grave weather results. Whereas, maritime atmosphere produces
gentle precipitation in contrast to the continental one.

Fig. 9.1 Simultaneous observation of sea salt particles and ice nuclei at
Jerusalem, Palestine.
Chapter 9
156
9.4
18
O and Deuterium (D) Contents of the Meteoric Water and Their
Characteristics.

18
O and D contents of water are expressed by the permille () deviation
of the isotope ratio from that of the reference water. The deviation is called
delta ( ) value, and Vienna-SMOW(Standard Mean Ocean Water), a
reference water distributed by IAEA(International Atomic Energy Agency), is
widely used.
The absolute isotope ratios of Vienna-SMOW are reported as follows.

D/H = ( 155.76 0.05 ) 10
-6
(Hagemann et al., 1970)

18
O/
16
O = ( 2005.20 0.45) 10
-6
(Baertschi, 1976)

The
18
O vs. D diagram of arbitrary rain group can be interpreted by the
implication of the plot pattern, which was clarified through the progress of
isotope hydrology in the latest three decades.
Following empirical equation, often called Craig plots (Craig, 1961),
was derived for D and
18
O,

D = 8
18
O + 10

from the analytical results of meteoric waters, implications were given to the
equation coefficients, generalizing Craigs equation as below (Dansgaard,
1964).

D = s
c
18
O + d

Dansgaard discussed sc and d of a suite of waters in a hydrologic system
to be determined by the extent of kinetic process in isotopic exchange during
evaporation/condensation. The s
c
was deduced close to 8 under
evaporation/condensation of equilibrated isotope exchange, but it deviated
from 8 to smaller values when the system went through non-equilibrium
process. d was explained to be determined by the initial evaporation condition
from the vapour source, water vapour, produced from the area where the
evaporation was intense. This tends to give a greater value of d to the
condensed water in equilibrium process, but vapour from the equilibrium
157
evaporation gives zero for d.
In general high D and
18
O level of natural water are found in arid region
due to the prevalence of intense evaporation. In such condition, D vs.
18
O
plots can have a smaller s
c
.

9.5 Some Case Studies

Two arid regions were surveyed (Wushiki, 1991 and 1993); but both
regions were still regarded as blank stretches in isotope hydrology, when the
work was planned.
In South Arabia, first the fieldwork was carried out in the North Yemen in
1976, and later in Northern Oman from 1982 to 1986. Following the two
foregoing works, Southern Oman was attempted in 1987. Eventually three
representative regions of South Arabia were brought into our knowledge with
characteristics reflecting the environment of each locality.
Tarim Basin, known as Taklamakan, is a great sandy desert in Chinese
Turkestan. Exploration was started in 1990 and three missions were sent
consecutively till 1992. Round the year change in isotopic ratios in the
meteoric waters were measured for the first time. Prior to these works, some
measurements were done by the Chinese Academy, but in a limited way.
However, further works are still left ahead.

9.5.1 South Arabia

9.5.1.1 Geographical Features

The geographical feature of South Arabia can be summarized as follows:
south-west and south-east coastline is fringed by steep slopes which culminate
in ridges of high altitude mountain range with the maximum point of ca. 3,700
m above sea level (a.s.l) in the Yemen. Its back-area extends inland decreases
the height gradually to form a great desertic plain. On the northeastern coast, a
detached mountain mass rises up along the Gulf of Oman and reach maximum
height of ca. 3,000 m a.s.l.
Precipitations prevail in the high-altitude area in the Yemen ca. 850mm/y,
max., but the inland-plain receives, less than 30mm/y. Eventually there is
more vegetation in the mountains, some part of which is covered by forest
densely under the influence of the south-western monsoon of the Indian
Chapter 9
158
Ocean.
Along the coast from the southwestern corner of the Arabian Peninsula to
the northeast, there are four traditional provinces: the Yemen, Hadhramaut,
Dhofar and Oman. The present study was carried out in three provinces among
the four, namely the Yemen, the Southern and Northern Districts of Sultanate
of Oman traditionally called Dhofar and Oman respectively. Figure 9.2 shows
the locations studied in this work.
Fig. 9.2 Rain sampling locations in South Arabia.

159
9.5.1.2 Sample Collection
In the Yemen, rain samples were collected at the airport of the capital
city, Sana'a (ca. 2,200 m a.s.l.), in 1977. Sampling site lies on the
northeastern slope of the Yemen Mountains the highest point of which attains
3,670 m a.s.l. at the peak of Al-Jabal al-Nabi al-Shuaib. Other related
natural waters were sampled in 1976/1977.
In Southern Oman, sampling sites were availed at two meteorological
stations; Salalah Airport and Qairoon Hairitti (ca. 850 m a.s.l.). Salalah
Airport is situated on the coast and Qairoon Hairitti is on the top of the Qara
Mountains just north of the airport. Rains were collected in 1988 and 1989,
especially in the earlier stage of the summer monsoon.
In Northern Oman, rain collection was done at a high altitude
hydrometeorological station in Saiq (ca. 1,800m a.s.l.) from 1988 and 1989
with some sporadic collections in the coastal and inland areas. Saiq is
situated at the southern face of the highest plateau of the West Hajar
Mountains, i.e., the Jabal al-Akhdhar, the crest of which rests at 2,980m a.s.l.
Each sample was collected from a single sequence of rainfall and not the
one accumulated through multi-sequence.

9.5.1.3 Results

1) Results in the Yemen
There are two distinguished rainy seasons sandwiching the summer
solstice caused by the shift in ITCZ. Monthly precipitation is shown in Fig.
9.3.
Stable isotope contents of the rain are plotted in
18
O and D diagram as
in Fig. 9.4. Generally the isotopic contents of the Yemeni rain are found at
high level and other natural waters take same tendency due to the rain.
However, the rainfall data are plotted well on the Craig plot. The rains in the
earlier rainy season tend to have heavier isotopes than later one. The weighted
annual average
18
O and D are 1.5 and -2.1 respectively.
Chapter 9
160

Fig. 9.3 Precipitation in Sanaa, Yemen.

Fig. 9.4
18
O and D of rain and other natural water in Yemen.
161
2) Results in Southern Oman (Dhofar)
There is a well-defined summer monsoon season, starts in June and ends
in September at Southern Oman. The south-western Indian monsoon blows in
Dhofar with damped air mass and produces fog and drizzle when it climbs up
the coastal ranges, i.e., the Qara and the Samhan Mountains. The highest
areas altitude of Samhan Mountains exceeds 1,400m a.s.l. Monthly
precipitations are shown with monthly rainy day's number in Fig. 9.5. Wet
season can be recognized clearly with the change of rainy day's number than
precipitation amount. Figure 9.4 includes rare occasions of cyclonic weather
emphasizing themselves over the monsoon rains unlike the usual year.
As presented in Fig. 9.6, Fig. 9.7, the isotope levels of the monsoonal rain
are quite high and averaged
18
O and D are +4.1 and +12.4 at Salalah
and -0.51 and +8.0 at Qairoon Hairitti respectively. In addition the
isotopic levels varied within remarkably narrow range, i.e.,
18
O and D
varied by 3 and 20 respectively. This aspect gives a contrast to the rains
in other seasons, which hold rather low level with wider range as given in Fig.
9.5.

Fig. 9.5 Precipitation in Salalah, Dhofar, Southern Oman.

Chapter 9
162

Fig. 9.6
18
O and D of rain in Salalah, Dhofar, Southern Oman.

Fig. 9.7 Daily change of
18
O and D of monsoonal rain in Dhofar, Southern
Oman. Salalah with solid circle and Qairoon Hairitti with open
circle.
163
3) Results in Northern Oman
In contrast to the above-mentioned two regions, Northern Oman is
influenced both by the southwestern summer monsoon and winter westerly
cyclic system. The monsoonal rains prevail exclusively in the high altitudes,
but the winter rains are rather frequent over the coastal plain. This seasonal
trend is apparent in Fig. 9.8 in which a typical coastal rain record at Seeb
Airport is superimposed on the Saiq record. Consequently the rainwater
isotope contents vary in a wider range than in the preceding two regions as
shown in Fig. 9.9.

Fig. 9.8 Precipitation in Saiq and Al-Rumais, Northern Oman. Al-Rumais
precipitation, solid column, is presented beside Saiq precipitation,
open column.

Chapter 9
164

Fig. 9.9
18
O and D of rain and other natural water in Northern Oman.

9.5.1.4 Discussion on the Results
The
18
O and D diagram of each regional rain group can be interpreted
by the plot pattern, which is discussed already in 3.
In case of the Yemen, isotopic plots of the rain, however, are found to have
similar plots like Craig plots, although they lie at the high level. High-level
plots are also found in the monsoonal rains both in Southern and Northern
Oman without much discrepancy from Craig plots. The level is sometimes
high enough to exceed SMOW, the origin point of the diagram. This kind of
isotopically enriched precipitation was observed in the Himalayas in the initial
stages of the summer monsoon, and the enrichment was attributed to the
difference in temperature between evaporation at the water vapor source and
condensation at the precipitation (Wushiki, 1977). The theoretical ground of
this phenomenon is derived from the experimental fact that isotopic
fractionation factors between water and vapor decrease with increase in
temperature, (Bottinga and Craig, 1969, and Majoube,1971). In such a
situation, lower temperature at the condensation level causes isotope
enrichment especially when precipitations are hardly formed before reaching
the high altitude due to the atmospheric system.
In arid region like Arabia, forced airlifting is one of the possible
mechanisms that cause the precipitation. And eventually there happens
similar process like in the Himalayas to produce isotopically enriched rains in
165
the mountainous areas. The proximity of the rain forming mountain area to
the vapor producing sea area, one of the geographical characteristics in the
Peninsula can enhance the tendency.
The narrowly ranged isotopic contents in the monsoonal rains in Southern
Oman are quite unique and this phenomenon indicates a steady rain-forming
mechanism of the monsoon system. This steady rain-forming mechanism
contributes greatly to the local hydrology and governs the ecosystem either
(Stanley Price et al. 1986). However, deep-born groundwaters were found to
hold pretty low isotopic levels and old 14C age (Clark et al., 1987), in spite of
their replenishing area which is identical with the present rainy area, i.e., the
coastal mountains. The
14
C datings of the groundwater, 20,000 to 30,000 years
before present (B.P.), suggests that different climatic systems have prevailed
in the past.
Such paleoclimatic condition was evidenced by paleolimnological study
(McClure, 1976), and deep sea core analyses (Fontugne and Duplessy, 1986,
and Niitsuma et al. 1991). At present global warming is presumed to be
under way due to anthropogenic causes, so it may intensify the Indian summer
monsoon in co-ordination with the heating of Tibetan Plateau (Yasunari, 1987).
This climatic shift may intensify the summer rains in Southern and Northern
Oman and increase isotopically enriched terrestrial waters there.

9.5.1.5 Conclusion

In this study, high
18
O/
16
O and D/H were found in the rains. But these
isotopically enriched rains did not show such evaporation effect that is
frequently found in arid region. In stead this enrichment was regarded as
caused by the local atmospheric process where rains were formed by the
forced air lifting in the high altitude area.
Narrowly ranged high level
18
O/
16
O and D/H were observed in the
summer monsoon rains in Oman. The narrow and steady level was attributed
to the steadiness of the summer monsoon system, which was just trapped by
the local geography. The difference in the isotopic contents between the
present rain and deep-born groundwater suggests the change of climate in the
past. Intensified southwestern Indian monsoon may result the global warming
and create a dominance of the isotopically enriched terrestrial waters in that
region.

9.5.2 Tarim Basin in Chinese Central Asia
Chapter 9
166

9.5.2.1 Geographical Features

The Tarim Basin is a land-locked basin and mostly occupied by the
Taklamakan Desert, the areal extent of which is ca. 327,000 km
2
. The basin is
surrounded by the world-famous high altitude ranges; Tianshan, Pamir and
Kunlun, in which some peaks reach higher than 7,000 m a.s.l. These high
altitude ranges are covered by glaciers extensively, indicating the orographic
effect to be a major factor in the regional hydrological regime. The fluvial
systems consequently heavily depend on the high altitude precipitation and
discharge into the basin, getting confluent as Tarim River. Tarim River
eventually ends up in Lake Lop Nor, a terminal lake widely known by the
name of Wandering Lake introduced by Sven Hedin, earlier in the 20th
century.

9.5.2.2 Sample Collection

Sample collections were carried out for three different categories, namely
precipitations, surface waters and ground waters. Surface waters include
river waters and lake waters. Most samples were collected by the field
activities executed every year in October from 1990 to 1992. Precipitation
waters were collected at the three temporary stations, installed with rain
gauges and snow sampling facilities; Nur at No.1 Cattle Farm on the foot hill
of the frontal mountains of the Eest Kunlun, Chira at the Desert Research
Station on the southern fringe of the Taklamakan Desert near Khotan, and
Batuan at the Meteorological Station near the confluence of Aksu River and
Tarim river. Sample collection was carried out by the local collaborators at
every occasion of precipitation throughout the year. Besides the precipitation
sampling, related meteorological data such as precipitation amount, its
duration and in situ atmospheric temperature were recorded. Some surface and
groundwater samples were kindly provided by some other scientists
concomitantly in exploration activity beside us. Simplified geographic features
and the exploration routes of the present work are shown in Fig. 9.10.
167

Fig. 9.10 Location map of the Tarim Basin.

9.5.2.3 Results

1) Groundwater
As a byproduct of satellite image study, we found a stretch of shallow
groundwater zone in Chira County of Khotan.
Stereoscopic visual scrutiny produced a sketch map which enabled us to
make access to the locations of surfacing sites of groundwater by the help of
GPS navigation. We could collect groundwaters from the two contrasting
ground surface areas; well vegetated and dune-covered.
Analytical results are presented in Fig. 9.11, where vegetated area is
represented by Chira, veget., and dune-covered and poorly vegetated areas
are by Chira Sands and Khotan Sands, and by Muji, respectively. They found
a tendency that shallow groudwaters under well-vegetated surface keep the
slope at 8, but in the dune-covered and poorly vegetated areas they tend to
distribute with slopes less than 8.

Chapter 9
168

Fig. 9.11
18
O vs. D of ground waters in the Tarim Basin.

2) River water
Seven conventional region-divisions were adopted for the sampling
localization; Keriya region, Khotan region, Kashgar region, Aksu region,
Kucha region, Korla region and Charchan region, as shown in Fig. 9.2.
Distribution range of the isotopic ratios was found at the highest level in
Khotan, Korla and Charchan regions, spanning -66.8 ~ -39.7 in D. Aksu
region fell on the second and Kashgar region on the lowest level, spanning
-79.1 ~ -72.7 and -88.7 ~ -78.3 , respectively.
Sc of lesser values in the
18
O and D diagram seem to prevail along
Charchan River and Aksu River than the other river courses concerned in
these results, Fig. 9.12.

169

Fig. 9.12
18
O vs. D of river waters in the Tarim Basin.

3) Lake water
Lake waters were collected in the peripheral high altitude areas of the
Tarim Basin. They gave a large diversity of isotopic ratio characterizing the
localities. In the Kokoshir Mountain region, the head of Charchan River, the
isotopic ratios of the original precipitation on the lake was estimated to be
-3.1 for
18
O and -14.8 for D.

4) Precipitation
Two round-year collections, in 1990/1991 and 1991/1992, were
successfully carried out in Khotan region, at Nur and Chira. And one
round-year collection was made at Batuan near Aksu. Total number of the
collected samples at Nur, Chira and Batuan are 56, 23 and 21, respectively.
The overall variation of D ranges a quite large span, which stretches
from polar to arid tropical as shown in Fig. 9.13, using the data from IAEA
(1986).

Chapter 9
170

Fig. 9.13 D ranges of precipitation in different locations.

The variation range is comparable to the Himalayan precipitation, quoted in
Fig. 9.5 from Wushiki (1977). Whereas, Nur precipitation for example, are
plotted in a two-component diagram, which appeared in a totally indigenous
pattern, Fig. 9.14.
First place, there is a sharp distinction between winter and summer with a
break at between April and May, in which winter precipitation is strongly
depleted, but summer one is enriched tremendously. The seasonal boundary
can be placed approximately at -15 and -100 for
18
O and D, respectively.
Second place, winter precipitation seems to precede isotope depletion
with the less d-index, and summer one seems to go just to the contrary.

171

Fig. 9.14 18O vs. D of precipitation at Nur, 1991/92.

9.5.2.4 Discussion on the Results

As reported above, several remarkable aspects were observed in the
isotopic composition of the samples. These may become convenient clues for
analyzing environmental change from the hydrological point.

1) Groundwater
In the preceding section, we mentioned that natural water is always
influenced to some extent by non-equilibrium isotope fractionation process.
As a result, water modified in a hydrologic cycle may assume particular
18
O
vs. D alignment. Craig et al. (1963) reported that such effect resulted from
free evaporation experiments in an open pan. Observed Sc of the isotopically
enriched residual water took the value from 4 to 6. However water in natural
porous matter, such as soil and sand, without surface vegetation, were found to
have Sc less than 4, when influenced by desiccation, Dincer et al. (1974).
Chapter 9
172
More extreme results were acquired by soil experiments, presenting Sc of
residual soil water at less than 2, Ohsumi (1984).
These extreme Sc values as caused by the bare surface; poor vegetation,
and under strong desiccation. The results obtained from shallow groundwater
under different surface vegetation may indicate the same phenomena. However,
more intensive and systematic work should be required before deriving any
conclusion for the applicability of this matter to the monitoring of regional
degradation of surface vegetation, i.e., desertification, through the property of
shallow groundwater.

2) River water
Fluvial system in the Tarim Basin is characterised by the fringing high
altitude mountains. Rivers originate in the glaciation zone and then flow down
the outskirt of the frontal mountains along a single flow course of a certain
length. So it is possible to pursue the isotopic enrichment of river water along
the flow course-avoiding disturbance of confluence. Enrichment proceeds
under an environmental effect; evaporation or desiccation. When
evaporation, i.e., desiccation, is intense, Sc, determined by isotopic
enrichment trend in the
18
O vs. D diagram, will be less.
In the present study, Sc of Aksu, Kucha and Charchan drainages are
smaller than that of Khotan, Keriya and Yarkand drainages. This result
implies that environment is more arid in the former drainages than in the
latter.
18
O vs. D corelations are not clear in Kashgar and Korla drainage where
irrigation canals are so complicated to establish a simple flow net.
Because the enrichment trend is established within the residence time of
river water in the flow passage concerned; supposedly only one or two days in
most cases, the present results are feasible only in this particular fieldwork
season, i.e., in October. Field surveys in other seasons could supplement the
general feature of this phenomenon.

3) Precipitation
The preliminary study brought a unique seasonal variation of the content
to light. But the mechanism behind this phenomenon is not yet investigated,
being focused on the two facts:

A) Summer precipitation tends to be enriched in heavy isotopes and attains
unusually high
18
O vs. D values of +40 and -1 , respectively, with very
173
high d-index showing little effect of post-formation evaporation.
Post-formation evaporation usually causes isotope enrichment and shift of
plots to the right of Craig plots.

B) Winter precipitation is depleted greatly and holds unusually low d-index,
which is an indicator of post-formation evaporation. But it is less probable to
have such effect in the winter environment.
The remarkable isotopic distinction between summer and winter
precipitations suggests different vapour origins for each seasonal group,
particularly characterised by the shift of d-index level. This distinction directs
our attention to the origin of the local river waters; which season dominates
the replenishment? Are they replenished by summer precipitation or winter?
Two river water groups, i.e., one from the northern side of the Kunlun
Mountains and the other from the southern side, are plotted and superimposed
on the precipitation diagram, Fig. 9.15. The superimposed positions of the
river water prescribe river waters in the locality to be replenished mainly by
summer precipitation.

Fig. 9.15
18
O vs. D of precipitation and river waters in West Kunlun
drainage.
Chapter 9
174

Winter precipitation appears at a greately depleted isotopic level, which
suggests a stronger affiliation to the westery atmospheric circulation and
provides most of the annual precipitation in the western neighbouring regions,
i.e., Afghanistan and Tajikistan, in winter. Such active weather causes large
isotopic depletion in the atmospheric vapour before their entry into the Tarim
Basin.
So far the discussion has dealt with southern side of the Basin, but the
environmental system seems to govern even the northern side. Figure 9.16 is
a diagram drawn for the precipitation collected at Batuan near Aksu.
Although the plots show some samples inflicted by the post-precipitational
evaporation, they again noticed a clear separation between summer and winter
precipitations. This identical aspect may confirm a larger areal extent for the
atmospheric system figured up by the present isotope study.

Fig. 9.16
18
O vs. D of precipitation at Batuan, 1991.

175
According to Wushiki (1981), d-indices of glacier ice and melt water vary
in zones along the circumferential mountains of Central Asian Plateau and
Basin Area.
In Fig. 9.17, d-index zones appear alternately with high or low values. As
for the higher d-index zones, Tianshan and Kunlun/Karakoram seems to be
connected in some way, and this connection is plausible when the results from
precipitation study are considered.
In addition, Yatagai et al. (1993) and Kitoh et al. (1993) reported a large
scale northery flow of atmospheric moisture over the Chinese part of Central
Asia in summer season. The results are regarded as the field proof for their
analyses.
It is impressive that Glaciers in the West Kunlun and Tianshan in Chinese
Central Asia are reportedly retreating, but those of the Kilen (Qilian)
Mountains are stationary or advancing, Xie(1993). This fact is again
supplementary for the large-scale moisture transport over the Tarim Basin in
summer.

Fig. 9.17 d-index distribution of glacier melt water inCentral Asia. City name
abbreviations: UR(Urumuchi), TSK(Tashkent), KB(Kabul),
KR(Karachi), KT(Kathmandu), LH(Lhasa), CD(Chengdu),
LZ(Lanzhou).
Chapter 9
176
9.5.2.5 Conclusion

Two hundred and fifty seven water samples, collected and analyzed so far,
which provided a insight into the hydrological system in the Tarim Basin,
although the study is still at the preliminary stage.
The isotopic data of shallow groundwater may provide semi-quantitative
clue to the deterioration of surface vegetation, i.e., desertification, through Sc
of local groundwater.
River waters can depict the local aridity through the isotope enrichment
trend along the river course. In case of the present study, they presented
regional tendency of temporary climate in October. But other season may
provide more diversity, and eventually establish isotope hydrological
monitoring method for regional climatic change.
The tremendous variation of isotopic composition in precipitation holds a
large potential applicability to the environmental research in and around the
Basin. The remarkable isotope enrichment in the summer precipitaion,
together with the affinity of local river water, confirmed local rivers to be
replenished mainly in summer season. And the precipitation suggested a
large-scale northerly moisture transport prevails in the Basin either in summer.

9.6 Conclusion and Future Prospect

Arid region is characterized by scarcity of water. Specifically, the region
has less incidents of precipitation. Consequently, the origin and the transport
trajectory of the atmospheric water are not easily traced, although some model
simulations have been attempted so far.
However, when the results of case studies are considered, isotope
hydrology seems to claim a great potential for providing ground clues to the
hydrological circulation models, acquired on arbitrary scientific disciplines. In
addition, the results above characterized the precipitation process in each
locality, which synoptic data could not clarify. Surface water was also found
modified of its isotopic composition by the local aridity, and the resulted
characteristics were regarded indigenous.
In arid region study, the progress in Isotope Hydrology has been greatly
achieved so far. However, recently new moves directed our attention to two
research fields: Dune sand hydrology and orographical effect focusing on fog.
Sand dunes have been regarded as substantial water reservoir since long
177
time ago. Conventional land-use is spreading there increasingly under the
local population pressure, but hydrological researches are still preliminary due
to the lack of methodology, particularly sounding and drilling. Coastal Deserts
are the region of dune sands, and more than three decades have passed since
Meigs published reviews on them (1966).
Local orography; mountains and hills, has attracted scientific interest in
its meteorological effect in the arid region, especially fog generation. When
the first international conference on fog and fog collection was held in
Vancouver, Canada, appreciable number of scientists attended there from the
arid region (Conference on Fog and Fog Collection (Canada), 1998). However,
they did not contribute from isotope hydrology unfortunately. As pointed out
in the case study, part of South Arabia is under the influence of Indian summer
monsoon. The coastal mountains are all in fog and drizzle then. It was
reported that more than 30 litters of water was collected per day by the 1 m2
fog collecting net. Isotope hydrology holds a realm in this particular region
and waits for pioneers.

References

Baertschi, P., Absolute 18O Content of StandardMean Ocean Water, Earth and
Planet. Sci. Lett., 31, 341-344, 1976.
Bottinga, Y. and Craig, H., Oxygen Isotope Fractionation between CO
2
and
Water, and the Isotopic Composition of Marine Atmospheric CO
2,
Earth
Planet. Sci. Lett., 5, 285-295, 1969.
Majoube, M., Fractionnement en oxygen 18 et deuterium entre leau et sa
vapeur, J.Chim.Phys. et Physico-Chim.Biol. 68, 1423-1436, 1971.
Clark, I.D., Fritz, P., Quin, O.P., Rippon, P.W., Nash, H. and Sayyid Barghash
bin Ghalib Al-Said "Isotope Technique in Water Resources Development",
IAEA, Vienna., 1987.
Conference on Fog and Fog Collection (Canada), Proceedings of First
International Conference on Fogand Fog Collection, Vancouver, Canada,
comp. And ed. Schemenouer,R.S. and H. Bridgman, 492p, 1998.
Craig, H.., Isotope Variation in Meteoric Waters, Science, 133, 1702-1703,
1961.
H., I
Chapter 9
178
Dansgaard, W., Stable Isotopes in Precipitation, Tellus, 16, 436-468, 1964.
Dincer, T., Al-Mugrin, A. and Zimmermann, U., Study of the Infiltration and
Recharge through the Sand Dunes in Arid Zones with Special Reference
to the Stable Isotopes and Thermonuclear Tritium, Jour. Hydrol., 23,
79-109, 1974.
Fontugne, M.R. and Duplessy, J., Variation of the Monsoon Regime during
the Upper Quaternary, Palaeogeogr. Palaeoclimatol. Palaeoecol., 56,
69-88, 1986.
Haagemann, R., Nief, G. and Roth, E., AbsoluteIsotope Scale for Deuterium
Analysis of Natural Waters, Absolute D/H Ratio for SMOW, Tellus, 22,
712-715, 1970.
IAEA, Environmental Isotope Data No.8: World Survey of Isotope
Concentration in Precipitation (19801983), Tech. Rep. Ser., No.264,
IAEA, Vienna., 1986.
Kitoh, A., Yamazaki, K. and Tokioka, T., Moisture Flux Climatology in the
Desert Regions in Western China, Proceedings of the Japan-China
International Symposium on the Study of the Mechanism of
Desertification, Tsukuba, 356-363, 1993.
McClure, H. A., Radiocarbon Chronology of Late Quaternary in the Arabian
Desert, Nature, 263, 755-756, 1976.
Meigs,P., Geography of Coastal Deserts, UNESCO, 140p., 1966.
Niitsuma, N., Oba, T. and Okada, M., Proc.ODP, Scientific Results, 117, 321,
1991.
Ohsumi, T., Personal communication, 1984.
Stanley Price, M.R., Ahmed bins Hamoud Al-Harthy, and Witcombe, R.P.,
"Arid Lands - Today and Tomorrow", Proceedings of an International
Research and Development Conference, Tucson, Arizona, U.S.A.,
Oct., 1985, Office of Arid Lands Studies, Univ. Arizona, Tucson, p.69.
1986.
Wushiki, H., Deuterium Content in the Himalayan Precipitation at Khumbu
District, Observed in 1974/1975, Seppyo, 39, 50-56, 1977.
Wushiki, H., Some Characteristics of Stable Isotope Content in the Himalayan
Waters, Geological and Ecological Studies of Qinghai-Xizang Plateau,
Vol.II, Proceedings of Symposium on Qinghai-Xizang(Tibet)
Plateau(Beijing, China), Science Press, Beijing, 1671-1676, 1981.
Wushiki, H., 18O/16O and D/H of the Meteoric Waters in South Arabia, Mass
179
Spectroscopy, 39, 239-250, 1991.
Wushiki, H., Takahashi, K., Masuda, A., Huang, Z. and Xiong, J., Isotope
Hydrological Features of the Tarim Basin, China, Proceedings of the
Japan-China International symposium on the Study of the Mechanism of
Desertification, Tsukuba, 380-395, 1993.
Xie,Z., Liu, C. and Ono, N., Fluctuation of Glaciers in Tianshan and
Qilianshan Mountains and Its Influence upon Desertification in Central
Asia, Proceedings of the Japan-China International Symposium on the
Study of the Mechanism of Desertification, Tsukuba, 25-35, 1993.
Yasunari, T., Gekkan Chikyu (in Japanese), 102, 685-690, 1987.
Yatagai, A. and Yasunari, T., The Precipitationand Water Vapour Transport
over and around the Arid and Semi-arid Regions of China, Proceedings of
the Japan-China International Symposium on the Study of the Mechanism
of Desertification, Tsukuba, 349-355, 1993.
Hot spring, Geothermal, Volcanic and Magmatic Waters
181
Chapter 10


10.1 Introduction

We had simple questions such as Where do hot spring waters come from?,
Where do volcanic gases come from?, How were ores formed?, What is the
ultimate origin of water in the Earths mantle?, etc. since long time. Stable
isotope geochemistry has answered, at least, part of these questions, since
hydrogen and oxygen isotopic ratios have been found very powerful tools in
identifying the source, origin and circulation of surface waters as discussed in the
previous chapters. In such discussions, we have learnt that the water isotopic
ratios change through mixing and isotopic fractionation associated with
evaporation and condensation during circulation and transport of ground waters,
river waters, lake waters, and even water vapor in the atmosphere. However,
thermal and volcanic waters have additional isotopic fractionation mainly due to
water-rock interaction that takes place under high temperatures. This will be
discussed in this chapter.
The origin of thermal waters has been vaguely thought to be a mixture of
groundwater with hot, deep-derived waters such as magmatic water or juvenile
water. Before going ahead, terminology of various waters should be defined.
Meteoric water is defined as water originated from meteoric precipitation (rain,
snow, polar ice, rivers, lakes and ground waters). Magmatic water is defined as
water present in magma regardless of its initial origin. Juvenile water is water
that has never appeared in the hydrosphere and comes from the deep interior of the
Earth such as mantle. Hence, the juvenile water is same as the mantle water.
Hot spring water is naturally occurring thermal water whose temperature exceeds
the local mean annual temperature. Geothermal water is water from wells that
were drilled to tap high temperature fluids for power generation and local heating.
Temperature of geothermal water at depth is significantly higher than the boiling
point of water at the surface of the Earth, and therefore geothermal water boils on
the way to the surface appearing as a mixture of liquid and vapor. Volcanic gases
are steam that comes out of fumaroles of volcanoes.
Chapter 10
182
Thermal and volcanic waters relate to their occurrence and do not specify
their origins. They may contain waters of various origins as defined above. In
the present chapter, we will discuss, in terms of stable isotopic signatures, the
origin of hot spring waters, geothermal waters, volcanic waters, magmatic waters,
and mantle waters.

10.2 Hot spring and geothermal waters

10.2.1 Hydrogen and oxygen isotopic compositions

In early days (before 60s) hot spring waters and geothermal waters
(collectively called thermal waters hereafter) were considered to contain a
significant proportion of magmatic or juvenile waters. In 1963 Harmon Craig
published an important paper which is now considered as a milestone in this field.
He postulated that thermal water is a mixture of local meteoric water with juvenile
water having uniform D/H and
18
O/
16
O ratios. This idea was shown in Fig. 10.1a
where it was assumed that the juvenile water had D= -2010 and
18
O =
82 . As described in Chapter 2, D and
18
O values of world meteoric waters
vary from a place to place but in a very consistent fashion with the relationship D
=
18
O + 10. This relationship is called meteoric water line (MWL) (Craig,
1961). On this basis, Craig expected that thermal waters from a given area
should plot on a tie line between a point on MWL and the juvenile water, resulting
in a fan-like distribution of the data points on a global scale. The measured data,
however, do not follow as Craig expected. Actual data points (Fig. 10.1b)
showed no convergence towards the juvenile water composition. They were
plotted almost parallel to the
18
O axis, showing enrichment only in
18
O relative to
the local meteoric water. This is called oxygen isotopic shift which is caused
by isotopic exchange of water oxygen with rock oxygen that has higher
18
O values
than the water. This will be discussed later under Section Oxygen isotopic shift.
The data points in Fig. 10.2 represent neutral thermal waters of mainly NaCl type.
Such waters are considered to be experienced prolonged water-rock interaction at
high temperatures during deep circulation of waters through the crust.
183

Fig. 10.1 Distribution of expected D and
18
O values of hot spring and
geothermal waters from different areas assuming that they are mixtures
of meteoric waters with juvenile water. The isotopic compositions of
the juvenile are assumed to be D = -2010 and
18
O = +82 .
Dashed lines indicate constant proportions (20 % and 40 %) of the
juvenile water. Modified from Craig (1963).

Fig. 10.2 Observed isotopic variations in NaCl type geothermal waters and steam
in geothermal areas. Solid points are the local meteoric waters, and
open circles are hot springs or geothermal waters from the areas
indicated. Reproduced from Craig (1963).
Chapter 10
184
The isotope geochemistry of Japanese hot spring waters was extensively
studied by Sakai and Matsubaya (1974). They grouped the hot spring waters into
4 types; (1) coastal, (2) highly saline, (3) Green tuff, and (4) volcanic.

(1) Coastal waters: The coastal type waters occur along the coast and are
essentially a mixture of seawater and local meteoric water. These waters are
generally high in temperature and salinity. Their chemistry is characterized by
high Na-Ca-Cl concentrations (3000~14000 ppm Cl
-
) and low SO
4
2-
concentration.
When a seawater-meteoric water mixture is heated, SO
4
2-
ion in seawater is
removed from the system as gypsum (CaSO
4
2H
2
O) due to low solubility of this
mineral at elevated temperatures. SO
4
2-
ion is also removed as magnesium
oxysulfate (Bischoff and Seyfried, 1978). Mg
2+
and Na
+
ions in seawater are also
removed whereas Ca
2+
and K
+
ions are added from rock leaching during
water-rock interaction. The experimental studies on basalt-seawater interaction
indicated that Mg
2+
was completely transferred into the hydrous alteration
products such as smectite, tremolite-actinolite, or talc, and net transfer of Na
+
from
sweater into solids occurred to form sodic-feldspar and analcime (Mottl, 1982).
The D-Cl
-
and D-
18
O relationships for the coastal type hot spring waters are
shown in Fig. 10.3. The D-Cl
-
relationship that goes through the points (D=0
and Cl
-
=19000 ppm) and (D=-36 and Cl
-
=0 ppm in this case) indicates that the
water is a mixture of seawater and local meteoric water. The
18
O-Cl
-

relationship, however, does not go through the point for seawater but slightly
higher
18
O values (a few ) were found. This isotopic enrichment is due to
oxygen isotopic exchange reaction between rocks and heated seawater at depths.
The chemical and isotopic changes during seawater-rock interaction observed
above are now widely recognized at submarine hydrothermal systems along the
mid-oceanic ridges and spreading axis of back-arc basins. The submarine
hydrothermal systems are one of the important factors that control the chemistry of
ocean water, because basalt-seawater interaction at spreading axes must have been
operating over geologic time. The hydrothermal fluids, resulting from the
water-rock interaction, are generally enriched in various metal ions and are
believed to represent ore-forming fluids for some massive sulfide/sulfate mineral
deposits such as Kuroko and Cyprus type ore deposits.
185

Fig. 10.3 (a) Relationship between d18O values and Cl- concentrations, and (b)
D-
18
O variations in Ibusuki hydrothermal system, a typical coastal
spring in Kyushu, Japan (Sakai and Matsubaya, 1974).

(2) Highly saline waters: This type of hot spring water is characterized by highly
saline Na-Ca-Cl-HCO
3
chemistry. A typical example of such waters was found
at Arima spa, near Kobe, Japan. The D-
18
O relationship is shown in Fig. 10 4
(Sakai and Matsubaya, 1974). The highest D and
18
O values are +6.5 and
28 , respectively. There is a linear relationship between
18
O values and Cl
-

concentrations with the highest Cl
-
at 43,790 ppm. This indicates mixing
between the local meteoric water and a highly saline brine of deep origin (Fig.
10.4b). The high salinity end-member may be related to magmatic water derived
from the upper Cretaceous to lower Tertiary granitic magmas of this region.
There is an alternative interpretation that these waters may represent brines
ascending through tectonic faults from deep sedimentary basins. Such brines are
known as connate waters that were enriched in dissolved chemical components
and in water isotopic compositions during slow migration of groundwater through
deep sedimentary rocks (Fig. 6.4 in Taylor, 1997).
Chapter 10
186

Fig. 10.4 (a) D-
18
O variations in the Arima hot spring, near Kobe, Japan, a
typical system characterized by highly saline waters (Sakai and
Matsubaya, 1974). (b) Relationship between
18
O values and Cl-
concentrations.
187
(3) Green tuff-type thermal waters: This type of waters is typically found at the
Green tuff regions in Japan. The Green tuff is a thick formation of volcanic rocks
of Tertiary submarine volcanism that distributes widely all over the country. The
D-
18
O relationship of this type of water is shown in Fig. 10.5. It is clear that
the D and
18
O values of these waters are almost identical to those of the local
meteoric waters, indicating that the Green tuff-type thermal waters are warm
groundwater that circulated through the Green tuff formations at relatively low
temperatures. The chemistry is of a Na-Cl-SO
4
type. The sulfate concentration
is generally high. Based on the
34
S and
18
O values, the sulfate seems be
derived from dissolution of anhydrite (or gypsum) that deposited from the Tertiary
seawater at temperatures higher than 110 C when it contacted with hot volcanic
rocks. The massive sulfide deposits of submarine origin, such as Kuroko, are
characterized by large deposition of anhydrite and gypsum.

Fig. 10.5 D-
18
O variations in the Green tuff-type thermal waters widely found in
the terrane of the Tertiary submarine volcanism in Japan (modified from
Fig. 4-15 in Sakai and Matsuhisa, 1996).

Chapter 10
188
(4) Volcanic thermal waters: Variety of thermal waters exists around
volcanoes ranging from an acid sulfate type to a neutral NaCl type. Figure 10.6
summarizes the D-
18
O relationship of volcanic thermal waters (Sakai and
Matsubaya, 1974). General features are (i) that the data plots along a line with an
approximate slope of 3 and (ii) each line starts from local meteoric water. Craig
(1963) explained these features by enrichment of heavy isotopes during kinetic
evaporation of local meteoric water at the surface. However, simple evaporation
of meteoric water would never create acid waters. Acid thermal waters around
volcanoes form as a result of condensation of volcanic steam containing CO
2
and
H
2
S at shallow depths. Such steam is produced at greater depths by liquid-vapor
separation of originally single phase magmatic fluids. The gases such as CO
2

and H
2
S are preferentially partitioned into a vapor phase. The vapor may be
injected into an aquifer of groundwater near the surface where oxidation of H
2
S by
atmospheric oxygen produces sulfuric acid. Assuming mass and isotopic
balances in a steady state, it was shown that the resulting water should have a
D-
18
O slope of ~3 (Giggenbach and Stewart, 1982).

Fig. 10.6 D-
18
O variations in volcanic thermal waters in Japan (modified from
Fig. in Sakai and Matsubaya, 1974).
189
The liquid phase, remaining at depths after subsurface evaporation, may be
enriched in dissolved salts. The behavior of fluids during the subsurface
evaporation is well illustrated by an enthalpy-salinity relationship as shown in Fig.
10.7. Let us assume that a deep single-phase fluid contains 1,100 ppm Cl- and
has a temperature of 300 C (i.e., enthalpy of 1,350 KJ/kg) as shown at point P
0
in
Fig. 10.7. The liquid phase would shift toward higher salinity and lower enthalpy
positions in Fig. 10.7 (P
1
and P
2
) as subsurface evaporation proceeds, since loss of
vapor will reduce enthalpy and enrich salinity of the liquid. High salinity thermal
water named Champaign Pool at the Waiotapu hydrothermal system, New
Zealand, may form in this way (Hedenquist and Henley, 1985). The vapor may
appear at the surface to form a steam-heated shallow thermal water reservoir
upon mixing with local groundwater (points WT3, WT4 and WT6). The isotopic
change caused by subsurface evaporation is discussed in some detail in the
following section.

Fig. 10.7 Enthalpy-salinity relationship at the Waiotapu hydrothermal system,
New Zealand (after Hedenquist and Henley, 1985). The trends of
waters that are produced by subsurface boiling with steam loss (P0
P2) and dilution of P1 by local groundwater are shown.
Chapter 10
190
10.2.2 Subsurface evaporation

The isotopic change caused by subsurface evaporation has been discussed in
detail by Truesdell et al. (1977). As hot water rises from depths to the surface, it
may reach a depth where temperature and pressure conditions allow evaporation
(or subsurface boiling) to occur. Steam phase, thus, formed can escape to the
surface in two modes; single-step steam separation and continuous steam
separation. In this paragraph, we will discuss the isotopic behavior during the
single-step steam separation.
Let us assume that the system consists of liquid and steam phases and that
isotopic equilibrium is always attained between the two phases (closed system).
As usual,
l
and
s
express the isotopic ratios of liquid phase and steam phase,
respectively. Fractionation factor
l-s
between liquid and steam is written as,

s
l
s l
r
r
(10.1)

where r
l
and r
s
are
18
O/
16
O (or D/H) ratios of liquid and steam in equilibrium,
respectively. From the definition of ,
3
tan
10 1

l
dard s
l
r
r

, and
3
tan
10 1

s
dard s
s
r
r
(10.2)
s l s l

ln 10
3

=
s l
(10.3)

As was shown in the section 1.3.1 in relation to this approximation, eq. (10.3) is
valid for small values, e.g., less than 15 . In the single-step steam
separation, the isotopic compositions of liquid and steam may be evaluated by an
isotopic mass balance equation;
191
0

l l s s
y y
(10.4)
1
l s
y y
(10.5)
) (
) (
0
l s
l
s
H H
H H
y
(10.6)

where H
l
, and H
s
are the enthalpies of liquid and steam at temperature T, and H
0
is
the enthalpy of the initial liquid before steam separation. y
s,
is a fraction of steam.
The value of y
s
is easily obtained from the enthalpy balance when available.
l

and
s
values are then obtained from combination of equations (10.3), (10.4) and
(10.5) as follows;

s l s l
y

0

(10.7)
s l s
y s
) 1 (
0

(10.8)
where
0,
is the initial isotopic composition of the single liquid phase before the
steam separation.
The isotopic variations can be calculated using the fractionation factors and
steam fractions given in Table 1 and are illustrated in Fig. 10.8 for subsurface
evaporation at 80 to 260 C of infiltrating meteoric water with the starting D

and
18
O

values of 54 and 8 , respectively. The slope S of the resulting
D-
18
O relationships is given by;

) 10 1 )( 1 (
) 10 1 )( 1 (
0
18 3
18
0
3
O
D
S
O
D

(10.9)

where
D
and
18O
are hydrogen and oxygen isotope fractionation factors between
liquid and steam at a given temperature (Horita and Wusdowskii, 1994), and D
0
and
18O
0
are the isotopic compositions of initial liquid. Upon evaporation liquid
becomes more and more enriched in heavier isotopes as y
s
value increases below
229 C. At this temperature the hydrogen isotopic fractionation becomes zero
and there is neither enrichment nor depletion in D/H ratio. This is called
cross-over. The isotopic compositions of steam, on the other hand, are lower
than the initial water, and the degree of isotopic depletion becomes less as y
s
value
0
18
O
Chapter 10
192
increases. The slope of the resulting liquid and steam, as calculated from
equation (10.9), changes from 5.8 at 80 C to 2.4 at 260 C with zero at the
cross-over temperature. At 374.13 C, a critical point of water, there is no
distinction between liquid and steam, and consequently the isotopic fractionation
disappears.

Fig. 10.8 Hydrogen and oxygen isotopic compositions of steam and liquid
separated under a closed condition at temperatures indicated from a
single liquid with D = -54 and
18
O = -8.0 . Solid and open
circles indicate the liquid and steam compositions, respectively,
calculated for steam fraction ys from 0.1, 0.2, 0.4 and 0.6. Note that a
liquid point with small ys is plotted close to the starting liquid
composition, whereas a steam point is plotted far away from the
starting point.
193
In nature the steam phase may not reside in a closed system. It may leak to
the surface through rock fractures. This means that the closed system assumption,
as discussed above, holds no longer. We will discuss continuous steam
separation where steam leaves as it forms. An equation for continuous steam
separation was given by Truesdell et al. (1977). When a small amount (m) of
steam is produced from water of mass m, the following equation is written for
conservation of energy;

) ( ) ( ) ( ) ( m m mH m m H m m m mH
s l l

(10.10)

where H
l
(m) etc. indicates the enthalpies of water and of steam of mass m.
Rearranging (10.10) and taking the limit as m goes to zero, we obtain
l s
l
H H
dm
dH
m ) (
(10.11)

Integrating (10.11) from initial (m
i
, H
l,i
) to final conditions (m
f
, H
l,f
) and using
the definition of remaining liquid fraction y
l
, we obtain

) ( ) ( exp
li h lf h s
H I H I y
(10.12)

where

l
ref
H
H l s
l
l h
H H
dH
H I
) (
) (

The integral is made from an arbitrary reference state. A similar equation is
obtained for conservation of isotopes;

l s
l
dm
d
m
) (
(10.13)

Integrating (10.13) from initial i to final conditions f;
Chapter 10
194
l
H
H
l s i l
f l
dH
H H
lf
li
)

=
+
+
) 1 / 1 (
) 10 (
) 10 (
ln
,
3
,
3
o
o
o
(10.14)

The above integral is made from H
l
,
i
to H
l,f
. Defining I as the integral from a
reference state (r) to a specified state (s),

l
H
H
l s
l
dH
H H
H I
l
ref
)

) / 1 1 ( 10
) (
3
o
(10.15)

where the integral is made from a reference state to a final state. Then,

| | { }
3
, ,
,
3
,
3
10 / ) ( ) ( exp
) 10 (
) 10 (
f l i l
i l
f l
H I H I =
+
+
o
o
(10.16)

The integrals I
h
and I(H
l
) are solved numerically and given in Table 1. From
equation (16) we can easily calculate the change in isotopic compositions of liquid
from the initial to final conditions. For detailed discussion see Truesdell et al.
(1977).

10.2.3 Oxygen isotopic shift

It is worthwhile considering the effect of water-rock interaction on the
isotopic compositions of thermal waters. To do this, we need to know a general
view about distribution of D and
18
O values of some typical crustal rocks as
shown in Fig. 10.9. The D values of metamorphic rocks are highly variable due
to contribution from a variety of sources. The D values of volcanic rocks are
also variable, because they change as a result of magma degassing or a mode of
magma emplacement as will be discussed later. However, we can find a certain
ranges of values for different types of the rocks (Fig. 10.9a). Volcanic rocks such
as basalts and andesites have a relatively narrow range of
18
O values that reflects
solidification at high temperatures. Granites have slightly higher values
reflecting solidification at lower temperatures and contribution of various source
materials, whereas sedimentary rocks have a wide range of variations and
generally characterized by very high
18
O values resulting from a variety of source
materials and low formation temperatures (Fig. 10.9b).
195

Fig. 10.9 Approximate ranges of D values (a) and
18
O values (b) of terrestrial
materials including meteoric water and rocks.

The water-rock interaction usually results in the oxygen shift, because (1)
oxygen isotopic composition of rocks is generally higher than that of meteoric
water (Fig. 10.9b), (2) the amount of oxygen in rocks, in contact with water, is
generally greater than that of water, (3) the amount of hydrogen in rocks is, in
general, much smaller than that of contacting water, and (4) oxygen isotopic
fractionation between silicates and water becomes smaller as temperature
Chapter 10
196
increases as shown later. The change in isotopic compositions of water and rocks,
in a closed system, can be calculated from the equation describing mass balance,
isotopic balance and isotopic fractionation (Sakai and Matsuhisa, 1996). The
isotopic mass balance equation may be expressed as,

f f i i
Y X Y X
(10.17)
rock f f water f f rock i i water i i
Y X Y X
, , , ,

(10.18)
water f rock f , ,

(10.19)

where X and Y stand for the exchangeable molar amounts of oxygen or hydrogen
in water and rocks, and i and f stand for initial and final states. is a convenient
approximation of the isotopic fractionation between rock and water. From
equations (10.17), (10.18) and (10.19), one can obtain,

) / ( 1
) ) / ( ) / ( (
, ,
,
i i
i f water i i i rock i
water f
Y X
Y Y Y X
(10.20)

The water/rock ratio may be easily understood by expressing it in terms of the
weight ratio. When W
i
grams of water reacts with R
i
grams of rock, X
i
/Y
i
ratio
equals (W
i
/R
i
)(16/18)/
i,
where
i
is the oxygen (or hydrogen) content of the rock.
For hydrogen, X
i
/Y
i
ratio equals (W
i
/R
i
)/
i,
where
i
is the water content of the
rock. Taking R
f
as the weight of rock after the reaction, R
f
= R
i
(1+(
f

i
)),
where
i
and
f
are the initial and final oxygen (or water) content of the rock,
respectively. Then, Y
f
/Y
i
= R
f
f
/ R
i
i
= (1+
f
i
)
f
/
i.
Putting these relations
into equation (10.20), a general equation describing the isotopic composition of
water after the water-rock interaction, can be written as

i i i
i f i f i i i water i rock i
water f
R W
R W
/ ) 18 / 16 )( / ( 1
) 1 ( ) / ( / ) 18 / 16 )( / (
, ,
,
(10.21)

For hydrogen an equation without term (16/18) in eq. (10.21) should be used.
Since approximately 50 wt.% of rock consists of oxygen, f /i = 1 can be assumed
197
in case of oxygen isotopic exchange during water-rock interaction, then equation
(10.21) becomes simpler. In the case of hydrogen exchange, however, final rock
usually contains more water than initial rock because of the formation of
secondary hydrous minerals during water-rock interaction. This results in the
increase in water content of the rock,
f
, which can be an order of magnitude
greater than
i
.
The oxygen and hydrogen fractionation factors for a variety of mineral-water
pairs have been experimentally and theoretically studied as a function of
temperature. Typical examples are shown in Fig. 10.10 for hydrogen (ONeil,
1986) and in Fig. 10.11 for oxygen (Taylor, 1979). The isotopic compositions of
water and rock, after water-rock interaction at 300C, were calculated as a
function of W/R weight ratio for a model system as shown in Fig. 10.12. The
model system consists of an initial rock having
18
O= +6.5 , D= -50 ,
f
=
i
= 50 % for oxygen,
i
= 0.5 %, and
f
= 3 % for hydrogen (as water), and initial
water having
18
O = -14 , D= -100 . The isotopic fractionation at 300C
was assumed as = +4.5 for oxygen and = -40 for hydrogen. Under high
W/R ratios (>0.5) the water isotopic compositions are close to the initial values,
and the rock isotopic compositions become highly depleted both in
18
O and D.
Under low W/R ratios (<0.05) the water values get closer to the initial rock values
but fractionated by , and the rock
18
O values do not change much from the
initial rock. Only D values become lower than the initial rock values. These
calculations indicate that the oxygen isotopic shift, often observed in thermal
fluids (Fig. 10.2), has been caused by water-rock interaction under W/R ratios
greater than 0.2. It should be noticed that, in natural systems, temperatures at
which water-rock interaction takes place can be variable and full isotopic
equilibrium, as assumed for the model calculations, may not be guaranteed.
Chapter 10
198

Fig. 10.10 Experimentally determined hydrogen isotopic fractionation factors for
some mineral-water pairs as a function of temperature (10
6
/T
2
).
Reproduced from ONeil (1986).
199

Fig. 10.11 Experimentally determined oxygen isotopic fractionation factors for
some mineral-water pairs as a function of temperature (10
6
/T
2
).
Reproduced from Taylor (1979).
Chapter 10
200

Fig. 10.12 Variations in equilibrium D and
18
O values of water and rock under a
closed system water-rock interaction at 300C as a function of W/R
weight ratio. Open circles indicate the initial compositions of water
and rock. Oxygen isotopic shift of water is expected for water that
interacted with rocks under low W/R ratios.

10.3 Magmatic and volcanic waters

10.3.1 D value of hydrogen in the mantle

The Earths mantle is a source of plutonic and volcanic rocks that constitute
201
the crust. The D value of hydrogen in the mantle, therefore, has a fundamental
importance in constraining the hydrogen isotopic evolution of crustal magmatism.
Search for the juvenile water discussed in the previous section (10-2-1) was
based on a belief that it should have a uniform isotopic composition within the
Earths mantle. The juvenile water is defined as water that resides in the mantle
and has never been appeared to the Earths surface. It is a conceptual existence,
but there have been many attempts to constrain the oxygen and hydrogen isotopic
compositions of the water based on observations on natural samples collected from
a variety of geologic settings. Oxygen isotopic composition of the water in the
mantle may be uniform as a first approximation, since it would be completely
controlled by overwhelmingly dominant mantle rocks under high temperatures.
The isotopic variations of hydrogen in the mantle can be variable and are reviewed
in this section.
The hydrogen isotopic composition of mantle hydrogen can be estimated
from the analysis of OH-bearing minerals that are considered to originate from the
mantle. Sheppard and Epstein (1970) and other researchers analyzed mantle
phlogopites and amphiboles and suggested that mantle water should lie in a
general range between 80 and 50 . These values are consistent with a
narrow range of D values (-80 to 60 ) reported by Boettcher and ONeil
(1980) for phlogopites from kimberlites and xenoliths. Some D values at the
higher end of the range may be contributed by water from subducted oceanic crust.
Large variations of D values (-125 to 12 ) in a very small scale (a few tens of
microns) were found by analysis using a secondary ion probe (SIMS), suggesting
contribution of waters from a variety of sources (Deloule et al., 1991).
D values of unaltered submarine basalt glasses can give another constraint
on the hydrogen isotopic composition of mantle water. Some of such data are
shown in Fig. 10.13 (Kyser, 1986). Submarine basalt glasses are formed when
basalt magma is quenched upon contact with cold seawater at the seafloor and are
believed to carry information of the original magma. As seen in Fig. 10.13, the
minimum D values lie in a restricted range of 80 5 , but many points tend to
distribute toward higher D values. The deviation towards more positive values,
as observed for the Kilauea samples, is interpreted to be due to contamination by
seawater at the time of magma extrusion. Loss of reduced hydrogen species like
H
2
and CH
4
results in the negative slope of the D-H
2
O relationship observed for
the Mid Atlantic Ridge basalts (MAR) and Galapagos Rise basalts (Galap) in Fig.
10.13. The lowest D values and H
2
O contents tend to cluster in a restricted
range of the values; D of about 80 and H
2
O of about 0.2 wt.%, indicating the
presence of a homogeneous reservoir of hydrogen in the mantle (Kyser, 1986).
Chapter 10
202

Fig. 10.13 Variations in D values and H
2
O contents of submarine basalts from
the Mid-Atlantic Ridge (MAR, open circles), Galapagos Rise (Galap),
the East Rift Zone of Kilauea (open squares), and tholeiites (solid
squares) and alkali basalts (solid triangles) from the Loihi seamounts.
The hatched zone indicates the range for the primary D values.
Reproduced from Kyser (1986).

10.3.2 Primary magmatic water

The primary magmatic water may be defined as water coexisting with magma
in chemical and isotopic equilibrium. The field for primary magmatic water
has been given by Taylor (1979). Because most volcanic and plutonic rocks have
a restricted ranges of D (-50 ~ -85 ) and
18
O (+5.5 ~ +10 ) values (Taylor
and Sheppard, 1986), and because crustal magmas exist in the approximate
temperature range from 700 to 1100 C, the isotopic compositions of primary
magmatic water can be calculated assuming attainment of full isotopic equilibrium
with minerals in magma. The isotopic compositions thus calculated have D
values ranging from 80 to 40 and
18
O values ranging from +5.5 to +9 ,
often referred to as the primary magmatic water or Taylors box in a D-
18
O
203
space.
This assumption, that full isotopic equilibrium with minerals, is attained in
the magma is acceptable for oxygen, since the
18
O of any exsolved fluid in
contact with the magma would be controlled by rapid exchange of oxygen isotopes
with a large reservoir of oxygen in the magma under magmatic temperatures. For
hydrogen, the assumption may not hold, because a large fraction of magmatic
water may be liberated by exsolution to form a H
2
O-rich fluid phase and fairly
large D/H fractionation is accompanied during the exsolution of water from the
magma. Nabelek et al. (1983) showed the whole rock D values of a granitic
stock decreased as H
2
O content of the rock decreased. This trend was interpreted
to be due to magma degassing or loss of D-enriched water from the magma.
Figure 10.14 plots the data together with the model calculations. Two models
were considered; (1) closed system degassing, and (2) open system degassing.
The closed system degassing assumes that degassed water always stays in contact
with the magma, whereas the open system degassing assumes that the degassed
water leaves the system as water exsolves from the magma. In the models, the
initial water content of 1.35 wt.%, D value of 50 and the D/H fractionation
factor of +30 were assumed. The data points in Fig. 10.14 are sandwiched by
the two model curves, suggesting that degassing proceeded under a semi-open
system. The oxygen isotope ratios of samples from the same granitic stock
remained almost constant at approximately +9 as expected.
Chapter 10
204

Fig. 10.14 Plot of whole-rock D values of rocks from the Notch Peak granitic
stock, Utah, as a function of logarithm of water content (ln(H
2
O)).
Data from Nabelek et al. (1983). Reproduced from Taylor (1986).

Similar changes in D values of volcanic glasses from explosive volcanic
eruptions are well documented (Taylor et al., 1983, Newman et al., 1989, Dobson
et al., 1989, Taylor, 1991, Wilding et al., 1993). Of these works the relationship
between H
2
O contents and D values for glasses collected from tephra and lava
flows of the 1340-1440 A.D. eruptions of Obsidian Dome volcano, California, is
shown in Fig. 10.15a and b. When a hydrous magma rises to a depth where the
205
magma is saturated with water, bubbles will form. The magma becomes a
mixture of bubbles and melt. This bubbly magma will rise further up due to a
decreased bulk density. At this stage water vapor in the bubbles stays in contact
with the melt. This situation may be modeled by a closed system degassing. If
the bubble/melt volume ratio exceeds a critical value of 3/1 (fragmentation curve
in Fig. 10.15a), the bubbles will be linked each other to form a H
2
O-rich gas phase.
High gas pressure may lead to an explosive eruption, releasing volcanic gases,
ashes and pumices to the atmosphere as often observed at the time of explosive
volcanic eruption. Part of the gas phase may escape from the system, resulting in
an open system degassing. After an explosive eruption ceases, water-saturated
magma is left behind. The water-saturated magma may rise again, creating the
same situation as before. In other words, multi-stage degassing may take place.
The D-H
2
O relationship for Obsidian Dome samples (Fig. 10.15b) suggests that
the multi-stage degassing was followed. Glasses in tephras from early eruptive
stages tend to have high H
2
O contents and high D values relative to later stage
samples. Lava flows, as observed in obsidian, show significantly lower H
2
O and
D values, suggesting that they were derived from a highly degassed magma.
The model curves in Fig. 10. 15b were calculated for closed system degassing and
open system degassing of a hydrous magma whose initial H
2
O content and D
being 4 wt.% and 40, respectively. The above two examples shown in Figs.
10.14 and 10.15 suggest that the D values of volcanic and plutonic rocks may
have been modified from their intrinsic values, and hence the D range for
primary magmatic water may be considered with some reservations.
Chapter 10
206

Fig. 10.15 (a) A model for degassing of rhyolitic magma. The lower curve
represents water saturation, and the upper one is a limiting curve for
fragmentation above which bubbles are liked to form a gas phase.
Arrows indicates explosive eruptions. (b) Relationship between D
values and water contents of glasses from Obsidian Dome, California
(modified from Taylor, 1991).

Experiments have shown that a large amount of water can dissolve in a
silicate melt. Water solubility increases as pressure of coexisting water vapor
increases, and also changes with the chemistry of melts. Recent in situ IR
measurements indicate that water in a melt exists in the form of H
2
O and OH
-

(McMillan, 1994). Experiments have also been done to determine the D/H
fractionation factors between water vapor and water dissolved in the silicate melts.
Since water in the melt exists as molecular H
2
O and OH hydroxyls and their
relative proportion changes with the total water content, the D/H fractionation
factor between water vapor and water dissolved in the melt (D
v-m
) is a function of
the water content. Recent experimental D
v-m
values for basaltic-andesitic melt
are ~40 at low H
2
O content (<0.5 wt.% corresponding to P
H2O
<20 bars) and
~16 at high water contents (6 to 9 wt.% at P
H2O
>3kb) (Pineau et al., 1998).
To model the hydrogen isotopic behavior of magma during degassing, more
precise data on the speciation and fractionation factor are required.

207
10.3.3 High temperature volcanic gases from arc volcanoes

As already shown in Fig. 10.6, the D and
18
O values of volcanic thermal
springs have commonly a trend that shows not only an oxygen isotopic shift but
also a hydrogen isotopic shift. This trend becomes more obvious when the
isotopic data of volcanic gas condensates collected from arc volcanoes are plotted.
Allard (1983) reviewed a data set that was available at that time and suggested,
based on the parallelism in D values of volcanic steam and local meteoric water,
that volcanic steam was originated from magmas that were contaminated by local
meteoric water. A new volcano named Showa Shinzan formed in 1944-1945 in
southern Hokkaido, Japan. It is a dome-forming dacitic volcano, typically found
in regions of convergent plate boundary. The D and
18
O values of high
temperature fumarolic gases from this volcano were continuously measured for
almost 20 years by Mizutani (1978) as shown in Fig. 10.16. He interpreted the
data by mixing of a magmatic water with D= -32 and
18
O= +7.4 and
oxygen shifted local meteoric water. The important point is that the extent of
oxygen isotopic shift of local meteoric water increased with time as a result of
water-rock interaction, whereas the isotopic signature of the magmatic water
remained unchanged. Kusakabe and Matsubaya (1983) first noticed that the D
and
18
O values of the Japanese high temperature volcanic gases from Satsuma
Iwojima, Kuju Iwoyama, Usu and Showa Shinzan clustered in a restricted range
(D being 3010 and
18
O being 5-8 ) regardless of the locality of the
volcanoes. They named this high D-
18
O water as HTVG (high temperature
volcanic gases). Exactly the same trends were also found for volcanoes such as
Merapi and Krakatoa in Indonesia, White Island in New Zealand, Soufriere in
Lesser Antilles (Allard, 1983) and several volcanoes in Kamchatka (Taran et al.,
1989). Taran et al. named these waters as andesitic water because they are
typically found in andesitic volcanoes. Giggenbach (1992) summarized these
isotopic features of volcanic water form volcanoes along the convergent plate
boundary (Fig. 10.17), and postulated the common existence of magmatic water in
andesite volcanoes having D of approximately 20 , much heavier than the
primary magmatic water and the assumed mantle water, as discussed above.
Giggenbach (1992) ascribed the origin of the andesitic water to dehydration of
sediments that were carried down beneath the arc by a subducting plate (Fig.
10.18). According to him, clay minerals, that formed during diagenesis in the
sediments, are characterized by D value around 30 , and the water squeezed
out of the sediments is involved in the genesis of andesitic magmas in the arc
environment. There is, however, a counterargument to Giggenbachs idea for the
Chapter 10
208
andesitic water. As discussed previously in the section of Primary Magmatic
Water, a large hydrogen isotopic fractionation (D
v-m
~ 20-40 ) is accompanied
when vapor phase is exsolved from a silicate melt. If the magma contains water
with D value of 60 and if it loses 0~40 % of water as a vapor phase, it is
possible to observe volcanic gases whose D values close to 20 ~ -40 . There
is no need to incorporate seawater-derived sedimentary materials in the genesis of
arc magmas (Matsuhisa, 1992).

Fig. 10.16 Isotopic variations of fumarolic condensates from Showa
Shinzan volcano, Hokkaido, Japan. Regression lines (1), (2)
and (3) are for samples collected during 1954-1959 (solid
circles), 1960 (open circles), and 1961 to 1963 (half-filled
circles), respectively. Some samples collected in 1968 and
1974 are included. Crosses indicate local meteoric waters.
Reproduced from Mizutani, (1978).
209

Fig. 10.17 The isotopic compositions of the most enriched water from a
given geothermal system, of fumarolic condensates from
andesitic volcanoes, and of local meteoric waters corresponding
to thermal waters. Lines parallel to the meteoric line represent
fractions of andesitic waters. Reproduced from Giggenbach
(1992).

Fig. 10.18 Giggenbachs view of the production of andesitic waters. Subducting
marine sediments are assumed to have D value of 3010 , and
fractionation during degassing gives rise to a composition of andesitic
waters of D= -2010 . Reproduced from Giggenbach (1992).
Chapter 10
210
References

Allard, P, The origin of hydrogen, carbon, sulphur, nitrogen and rare gases in
volcanic exhalations: Evidence from isotope geochemistry. "Forecasting
Volcanic Events", edited by H. Tazieff and J.-C. Sabroux, Development in
Volcanology, 1, p. 337-386. Elsevier, Amsterdam. pp. 635, 1983.
Bischoff, J.L. and W.E. Seyfried, Hydrothermal chemistry of seawater from 25 to
350C, Am. J. Sci., 278, 838-860. 1983.
Boettcher, A.L. and J.R. ONeil, Stable isotope, chemical and petrographic studies
of high-pressure amphiboles and micas: Evidence for metasotism in the
mantle source regions of alkali basalts and kimberlites, Am. J. Sci., 280A,
594-621, 1980.
Craig, H., Isotopic variations in meteoric water, Science, 133, 1702-1703, 1961.
Craig, H., The isotope geochemistry of water and carbon in geothermal areas,
Nuclear Geology on Geothermal Areas, edited by E. Tongiorgi. Spoleto, 1963.
p. 17-53, 1963.
Deloule, E., F. Albarede and S.M.F. Sheppard, Hydrogen isotope heterogeneities
in the mantle from ion probe analysis of amphiboles from ultramafic rocks,
Earth Planet. Sci. Lett., 105, 543-553, 1991.
Dobson, P. F., S. Epstein, and E.M. Stolper, Hydrogen isotope fractionation
between coexisting vapor and silicate glasses and melts at low pressure.
Geochim. Cosmochim. Acta, 53, 2723-2730, 1989.
Giggenbach, W.F., Isotopic shifts in waters from geothermal and volcanic systems
along convergent plate boundaries and their origin, Earth Planet. Sci. Lett.,
113, 495-510, 1992.
Giggenbach, W.F. and M.K. Stewart, Processes controlling the isotopic
composition of steam and water discharges from steam vents and
steam-heated pools in geothermal areas, Geothermics, 11, 71-80, 1982.
Hedenquist, J.W. and R.W. Henley, Hydrothermal eruptions in the Waiotapu
geothermal system, New Zealand: Their origin, associated breccias, and
relation to precious metal mineralization, Econ. Geol., 80, 1640-1668, 1985.
Horita, J. and D.J. Wesolowski, Liquid-vapor fractionation of oxygen and
hydrogen isotopes of water from the freezing to the critical temperature,
Geochim. Cosmochim. Acta, 58, 3425-3437, 1994.
Keenan, J.H., F.G. Keyes, P.G. Hill, and J.G. Moore, Steam Tables
thermodunamic properties of water including vapor, liquid, and solid phases
(International Edition), John Wiley, New York, 162 p, 1969.
211
Kusakabe, M. and O. Matsubaya, Volatiles in magmas, volcanic gases, and
thermal waters, Bull. Volcanol. Soc. Japan, 30, S267-S283 (in Japanese),
1983.
Kyser, T.K., Stable isotope variations in the mantle, J.W. Valley, H.P. Taylor and
J.R. ONeil eds: Stable Isotopes in High Temperature Geological Processes
(Reviews in Mineralogy, Vol. 16). Chapt. 5, p. 141-164. pp. 570, 1986.
Matsuhisa, Y., Origin of magmatic waters in subduction zones: Stable isotopic
constraints, Rept. Geol. Surv. Japan, No. 279, 104-109, 1992.
McMillan, P.F., Water solubility and speciation models, M.R. Carroll and J.R.
Holloway eds: Volatiles in Magmas (Reviews in Mineralogy, Vol. 30). Chapt.
4, p. 131-156. pp. 517, 1994.
Mizutani, Y., Isotopic compositions of volcanic steam from Showashinzan volcano,
Hokkaido, Japan, Geochem. J., 12, 57-63, 1978.
Mottl, M.J., Hydrothermal processes at seafloor spreading centers: application of
basalt-seawater experimental results, "Hydrothermal Processes at Seafloor
Spreading Centers", edited by Rona, Bostrom, Laubier and Smith, NATO
Conference Series, IV: Marine Sciences, p. 199-224, Plenum Press, New York,
1982.
Nabelek, P.I., J.R. ONeil, and J.J. Papike, Vapor phase exsolution as a controlling
factor in hydrogen isotope variation in granitic rocks: the Notch Peak granitic
stock, Utah, Earth Planet. Sci. Lett., 66, 137-150, 1983.
Newman, S., S. Epstain, and E. Stolper, Water, carbon dioxide, and hydrogen
isotopes in glasses from the ca. 1340 A.D. eruption of the Mono Crater,
California: Constraints on degassing phenomena and initial volatile content,
Jour. Volcanol. Geothermal Res., 35, 75-96, 1988.
ONeil, J.R., Theoretical and experimental aspects of isotopic fractionation, J.W.
Valley, H.P. Taylor and J.R. ONeil eds: Stable Isotopes in High Temperature
Geological Processes (Reviews in Mineralogy, Vol. 16). Chapt. 1, p. 1-40. pp.
570, 1986.
Pineau, F., S. Shilobreeva, A. Kadik, and M. Javoy, Water solubility and D/H
fractionation in the system basaltic andesite-H
2
O at 1250C and between 0.5
and 3 kbars, Chem. Geol. (Isotope Geoscience), 147, 173-184, 1998.
Sakai, H. and O. Matsubaya, Isotopic geochemistry of the thermal waters of Japan
and its bearing on the Kuroko ore solutions, Econ. Geol., 69, 974-991, 1974.
Sakai, H. and O. Matsuhisa, Stable isotope geochemistry, University of Tokyo
Press, Tokyo. 403 p, 1966 (in Japanese).
Sheppard, S.M.F. and S. Epstein, D/H and
18
O/
16
O ratios of minerals of possible
mantle or lower crustal origin, Earth Planet. Sci. Lett., 9, 232-239, 1970.
Chapter 10
212
Taran, Yu. A., B.G. Pokrovskiy, and Yu. M. Dubik, Isotope composition and origin
of water in andesite magma, Transactions (Doklady) of the USSR Academy of
Science, 304, 199-202, 1989.
Taylor H.P., Oxygen and hydrogen isotope relationships in hydrothermal mineral
deposits, Geochemistry of Hydrothermal Ore Deposits, 2nd edition (Chapt.
6, p. 236-277), H.L. Barnes ed., John Wiley and Sons, New York. pp. 798,
1979.
Taylor H.P., Oxygen and hydrogen isotope relationships in hydrothermal mineral
deposits, Geochemistry of Hydrothermal Ore Deposits, 3rd edition (Chapt. 6,
p. 229-302), H.L. Barnes ed., John Wiley and Sons, New York. pp. 972, 1997.
Taylor, H.P. and S.M.F. Sheppard, Igneous rocks: I. Processes of isotopic
fractionation and isotope systematics, J.W. Valley, H.P. Taylor and J.R. ONeil
eds: Stable Isotopes in High Temperature Geological Processes (Reviews in
Mineralogy, Vol. 16). Chapt. 8, p. 227-271. pp. 570, 1986.
Taylor, B.E., Magmatic volatiles: Isotopic variation of C, H, and S, J.W. Valley,
H.P. Taylor and J.R. ONeil eds: Stable Isotopes in High Temperature
Geological Processes (Reviews in Mineralogy, Vol. 16). Chapt. 7, p. 185-225.
pp. 570, 1986.
Taylor, B.E., J.C. Eichelberger, and H.R. Westrich, Hydrogen isotopic evidence of
rhyolitic magma degassing during shallow intrusion and eruption, Nature, 306,
542-545, 1983.
Taylor, B.E., Degassing of Obsidian Dome rhyolite, Inyo volcanic chain,
California, Stable Isotope Geochemistry: A Tribute to Samuel Epstein (eds.
H.P. Taylor, J.R. O'Neil and I.R. Kaplan), The Geochemical Society, Special
Publication No. 3, p.339-353, 1991.
Truesdell, A.H., M. Nathenson, and R.O. Rye, The effects of subsurface boiling
and dilution on the isotopic compositions of Yellowstone thermal waters, Jour.
Geophys. Res., 82, 3694-3704, 1977.
Wilding, M.C., R. Macdonald, J.E. Davies, and A.E. Fallick, Volatile
characteristics of peralkaline rhyolites from Kenya: an ion microprobe,
infrared spectroscopic and hydrogen isotopic study, Contrib. Mineral. Petrol.,
114, 264-275, 1993.

Sampling of fluids involved in hydrothermal system
213
Chapter 11 (Practice 1)


11.1 Volcanic gas

11.1.1 Property of volcanic gas

One of the important properties of volcanic gas, which should be
considered at the time of sampling, is that it has the high enthalpy. In general,
the most abundant composition in volcanic gas is water vapor. We sample
volcanic "gas" as condensate. Therefore, at the sampling site, the enthalpy of
water vapor must be reduced by cooling.
The temperature of volcanic gas ranges from the local boiling point of
water to the magmatic temperature, namely, of about 900 C. A volcanic gas
contains air in a large proportion temperature lower than the local boiling
temperature.
The condition of the gas discharge is variable. A strong discharge of
volcanic gas makes the sound similar to a jet engine. The strong sound could
make our talk impossible even if we speak loudly. Such a strong volcanic
gas may throw out a piece of rock from fumarole. The strong discharge of
"gas" sometimes involves a liquid water phase. The bulk enthalpy of such a
"fluid" is lower than the enthalpy of the dry water vapor with the same
temperature. The low enthalpy of the fluid suggests a high pressure of gas
source.
A moderate discharge of volcanic gas is defined here as the discharge
with no strong sound, and to be discharged with a raising steam and definitely
can be identified 20-30m far from the fumarole. The moderately discharging
volcanic gas is suitable for the sampling of isotopic study. A weak discharge
of volcanic gas may be defined as the discharge with a raising steam which
can not be identified from 20-30m far from the fumarole. The water vapor
contained in the weak discharge shows frequently a depleted D and
8
O due
to a liquid water loss. A weak volcanic gas is not recommended to be
sampled, if you can find a moderate or a strong fumarole in the target field.
214
The concentration of gas species other than H
2
O is variable. Carbon
dioxide and H
2
S, SO
2
, HCl are often contained with high concentration in
volcanic gas. Those gases have toxicity. Some protections, for example, a
gas mask is necessary if the concentration of those species is high.
The
8
O value of the condensate of the volcanic gases with low CO
2

concentration is thought to be identical to the
8
O of H
2
O. If CO
2

concentration is high, the
8
O of H
2
O will be modified due to the
8
O
fractionation between CO
2
and H
2
O (Mizutani et al. 2000). The water
condensate is slightly depleted in
8
O because of the preferential distribution
of
8
O to CO
2
gas. For a precise isotope study, the depleted
8
O value of
water condensate must be corrected based on the
8
O of CO
2
gas.

11.1.2 Apparatus for the sampling

Volcanic gases discharging from fumarole is introduced to a condenser
using a titanium tube. Titanium is used because it can withstand to HCl, SO
2

and H
2
S that are by volcanic gas. However, titanium is corroded by HCl gas
at the temperature higher than 500 C. In case of high temperature volcanic
gas, silica glass tube is used for gas introduction.
Various types of condenser have been used by researchers for the
collection of H
2
O condensate. In Fig. . one of condensers is described.
The merit of the condenser, shown in Fig. ., is the simplicity of the
structure and easily to clean. The condenser is made of Pyrex glass. The
inner part can be separated from the outer tube.
The major parts of the sampling system are the tube for the introduction
and the condenser. Other small parts necessary for the sampling are
described in the next section.
215

Fig. 11.1 Condenser made of Pyrex glass. a: inlet mouth, b: outlet mouth,
c: outer tube which can be separated from inner part.

11.1.3 Sampling and Measurements

Figure .2 shows the arrangement of apparatus for the sampling. The
volcanic gases from fumarole is introduced by a titanium or a silica glass tube.
A flexible rubber tube is connected to the end of the introduction tube. If the
volcanic gas contains large air, then pre-cooling section is necessary. The
pre-cooling section is composed of a long rubber tube which is immersed in a
chilled water. If the air contamination in volcanic gas is small, the
pre-cooling section is not necessary. After the pre-cooling section, a choke is
placed on the rubber tube. With a use of simple screw stop cock the rubber
tube can be choked. The choking is necessary if the pressure of volcanic gas
is too strong and the flow rate of volcanic gas in the tube is too large. After
216
the choke, the condenser is connected. The condenser is placed in a plastic
cup filled with cold water. About liter of cool water is necessary for the
collection of condensate with volume of 20-30 ml. The condenser is
connected to a air pump through a rubber tube. The rubber tube is connected
to the suction air pump. Any pump can be used for this purpose.
The volcanic gas is introduced to the condenser with the operation of air
pump. During the sampling, we check the temperature of condensate
touching the outlet mouth of the condenser (i; Fig. .2). The temperature of
the outlet mouth must be less than about 40 C. If the sampling rate is too
high, the condensate collected in the condenser becomes hot, leading a partial
evaporation. The partial evaporation modifies the isotope ratio of condensate.
If we feel that outlet mouth is becoming hot then the speed of pumping
operation is reduced.
How can we know the air contamination in volcanic gas? First we try a
sampling without the pre-cooling section. If the air contamination in
volcanic gas is significant, the sampling rate of condensate will be very low
relative to the case of little air contamination. If the air contamination is small,
it takes about 0 minutes to collect 20 ml of condensate.
When we collect several ml of condensate, the sampling is suspended.
Then inner part of the condenser is separated and the collected condensate is
discarded. The discarded condensate have been used for the cleaning the
inside of the tubes. After the discard, the sampling is restarted. For the
conventional isotope analysis, 20 ml is required. For the tritium analysis, at
least 00ml of condensate is needed.
The collected condensate is carefully transferred to a storage bottle.
Storage bottle is a small glass bottle with a screw cap made of a hard plastic.
A conventional, relatively inexpensive polyethylene bottle is not good for a
long term storage. If the cap had been fastened too strong, the cap of
polyethylene bottle will be broken over ten years of storage, as shown in Fig.
.3. After or before the sampling of condensate, the temperature of volcanic
gas is measured with a digital thermometer.
In general, the sampling and analysis of volcanic gas is complicated and
we need practice. The details of the sampling and analysis for chemical
composition of volcanic gas is described by Giggenbach and Goguel (989).

217

Fig. 11.2 The arrangement of apparatuses for the sampling of volcanic gas
condensate. a: fumarole, b: titanium or silica glass tube for
introduction of gas, c: connector, d: flexible rubber tube, e:
pre-cooling system composed from a long rubber tube immersed in
a water box with ice blocks, f: screw stop cock for the choking of
rubber tube, g: condenser, h: coolant water, i: outlet mouth of
condenser, j: suction air pump.

Fig. 11.3 A bottle for sample water storage with a broken cap. a: broken point,
b: screw cap, c: sealing cap.
218
11.2 Geothermal fluid

11.2.1 Property of geothermal fluid

The bulk enthalpy of the fluid from geothermal wells is relatively lower
than the enthalpy of dry water vapor, because of the involvement of liquid
water phase. This feature is similar to the property of volcanic gas with high
pressure. The isotope analysis should be done for both the vapor and liquid
water. The relative isotope ratio of vapor to liquid water gives the bulk isotope
ratio of geothermal fluid.

11.2.2 Apparatus of the sampling

The vapor phase in the geothermal fluid can be sampled through a
vapor-liquid separator. The apparatus used for the sampling of volcanic gas
condensate can also be used for the sampling of the vapor from geothermal
well. The geothermal fluid has an enough pressure, hence air suction pump
is not necessary. For the sampling of liquid phase, no special apparatus is
needed.

11.2.3 Sampling and Measurements

If the flux of steam from separator can be adjusted to the apparatus of
sampling, the rubber tube may be directly connected to the outlet mouth of
separator. If the flux of steam is too large, the flux can not be adjusted then
the direct connection is not recommended. Instead of the direct connection,
the tube for introduction (b; Fig. .2) is inserted into the outlet mouth of
separator. With the insertion, an excess steam is abounded through the
opening between the tube and the outlet mouth.
The bulk isotope ratio of fluid should be known to study geothermal fluid.
The flux ratio of vapor to liquid water should be measured for the calculation
of bulk isotope ratio of geothermal fluid.

11.3 Crater lake water

11.3.1 Property of active crater lake water

219
Active crater lakes are part of the hydrothermal system of volcano
(Kusakabe 994, Varekamp and Rowe 2000). The lake water temperature is
definitely higher than the ambient air temperature. The lake water contains
specific components such as F
-
, Cl
-
and SO
4
2-
with volcanic origin. The lake
water is often strongly acidic. The isotopic ratio of active crater lake water
will show an enrichment relative to the local meteoric water. Small crater
lakes develops an effective convection in the lake water with heat supply at
the bottom, result in homogenized lake water. On the other hand, most of the
large crater lakes would have a heterogeneity in the composition.
The lake water in active craters originates mostly from local meteoric water
with some contribution of magmatic water. Due to the elevated lake
temperature, the lake water suffers significant evaporation. The evaporation
from the lake surface brings an isotope enrichment.
The D and
8
O enrichment by the evaporation effect is indicated by a shift
directed upper right on the conventional D vs.
8
O plane. This movement
is similar to the isotopic shift of lake water brought by the addition of
magmatic water. The isotopic enrichment, observed in the lake water, would
be due to those two contributions. Based on only isotope analysis, the two
contribution can not be separated clearly, however, if the Cl
-
concentration of
lake water is considered, the contribution from magmatic water can be
evaluated (Ohba et al. 2000). In this sense, volcanic Cl
-
or other components
are recommended to be analyzed with the isotope ratio of lake water.


The lake water may have a heterogeneity in the composition. The
samplings of lake water should be made at the different depths at different
positions on lake.
The sampling of lake water from depth is carried out by the sampler
shown in Fig. .4. The Van-Dorn water sampler collects a water sample
even from the depth of 00 m below the surface. We use a single loop to
hang the Van-Dorn sampler. To close the upper and bottom caps of the
sampler, a weight called as "messenger" is dropped along the hanging loop.
If the sampling depth is shallow, a simple handmade sampler shown in Fig.
.4(b) might be used. The sampler has a string for the opening of inlet
mouth. An additional string is necessary other than the hanging loop of
sampler. Pulling out the string, lake water is introduced into the sampling
bottle. The surface water of lake is sampled with the use of a dipper. The
220
use of a dipper made of metal should be avoided. A plastic dipper is
desirable.

Fig. 11.4 (a) Van-Dorn type water sampler. (b) A handmade water sampler.
: rubber cap, 2: messenger, 3: hanging loop, 4: loop to weight,
5: sampler body, 6: rubber tube which is removed with a string
from boat, 7: short glass pipe for the discard of air, 8: long glass
pipe for the introduction of water.
221
11.3.3 Measurements

When we take a water sample with the Van-Dorn sampler, the water
temperature must be measured on a boat immediately after the salvage of
sampler. Sampling point of lake water is determined with a help of map, if
the point is close to lake shore. However, when the sampling point is far
from the shore, the determination of the sampling point is not easy. Recently
an inexpensive handy GPS meter became available. The small GPS meter is
used for the positioning of sampling point on the boat.

11.4 Hot spring water

11.4.1 Property of hot spring water

Hot spring water and a cold mineralized spring water dissolve anions with
volcanic origin and cations with country rock origin. The isotope ratios of
those water closes to the local meteoric water in the most cases. A small
isotopic deviation from the local meteoric water will be interpreted to be a
interaction of country rock or a addition of magmatic water or a difference in
the isotope ratio of recharge water. If isotopic deviation relative to local
meteoric water show a correlation to the concentration of volcanic components
such as Cl
-
, the contribution of magmatic water is implicated. Some
hydrothermal system involves a fossil sea salt or fossil sea water. The
contribution of those fossil components show a feature similar to the
contribution of magmatic fluid (Matsubaya and Sakai, 989).
High temperature hot spring water associated with steam discharge show
occasionally a significantly enriched isotopic ratios. The enriched isotopic
ratios is explained to be the liquid phase equilibrated with the steam. The
enrichment may also be due to the partial evaporation of hot spring water.


The apparatus for the sampling of water is only a plastic dipper and metal
one should be avoided. In the case that the flow rate of water is very low, a
syringe is useful to the effective collection of water. We can suck the water
into a syringe putting the mouth of syringe to the outlet of water discharge.

222
11.4.3 Measurements

The temperature of spring water is measured at the outlet point. With
the use of rod type sensor, the variation in the temperature of spring water is
examined, if there are several discharging points. The maximum in the
temperatures is recorded. The sampling and analysis of water from geothermal
system is described in details by Nicholson (993).

References

Giggenbach, W. F., and Goguel, R. L., Collection and analysis of geothermal
and volcanic water and gas discharges. CD 240, Chemistry Division,
Department of Scientific and Industrial Reserch (DSIR), Petone, New
Zealand, 989.
Kusakabe, M., Geochemistry of crater lakes (Special issue of Geochem. J.)
The Geochemical Society of Japan, 306, 994.
Matsubaya, O. and Sakai, Y., On a high saline brine of meteoric origin from
Ohdo, Gunma, Japan. Water-Rock interaction, WRI-6 Malvern, UK,
Miles, D.L. Ed. Balkema, 465-467, 989.
Mizutani, Y., Sasaki, Y., Hori, M., and Koyama, M., Chemical compositions
and isotopic ratios of fumarolic gases and hot spring waters from
Tateyama-jigokudani, Toyama, Japan. Chikyukagaku, 34, 77-89, 2000.
Nicholson, K., Geothermal fluids, Chemistry and Exploration Techniques,
Springer-Verlag, Berlin, 993.
Ohba, T., HIrabayashi, J., and Nogami, K., D/H and
8
O/
6
O ratios of water in
the crater lake at Kusatsu-Shirane volcano, Japan.
J.Volcanol.Geotherm.Res., 97, 329-346, 2000.
Varekamp, J. C., and Rowe, G. L., Crater lakes (Special issue of
J.Volcanol.Geotherm.Res.), Elsevier, Amsterdam, 508, 2000.

Hydrological and hydrochemical characteristics of rainfall, throughfall, stemflow
and streamwater in the University Forest in Chiba, the University of Tokyo
223

Hydrological and hydrochemical characteristics of rainfall,
throughfall, stemflow and streamwater in the University Forest in
Chiba, the University of Tokyo

12.1 Introduction and site description

12.1.1 General introduction of the University Forest in Chiba

The University Forest in Chiba, located in the southern part of the Boso
Peninsula, was established in 1894 and is the oldest university forest in Japan
(Figure 12.1). The total area of the forest is 2,171 ha. The mean annual
temperature is 14.2 C and the mean monthly temperature in midwinter and
midsummer is about 4 C and 25 C, respectively. This university Forest is made
up of various kinds of experimental plots, protection forests and demonstration
forests of indigenous and exotic species. They are used for field studies into
various aspects of forest science.
There are three experimental fields in the context of forest hydrological and
forest micro-meteorological studies i.e., Fukuroyamasawa Experimental
Catchments, Do-sawa Experimental Catchments and Shinta Micrometeorology
Observation field.

12.1.2 Fukuroyama-sawa Experimental Watershed

Fukuroyama-sawa Experimental Watershed, situated about 60 km SE of
Tokyo at 3512 N and 14006 E, elevation 124-227 m, was established in 1991
to study the influence of logging on rainfall runoff processes by a paired
watershed approach (Figure 12.2). The main watershed (2.03 ha) consists of three
smaller watersheds; sub-watershed A (0.80 ha), sub-watershed B (1.09 ha) and the
residual watershed. Three stilling pools with V-notch weirs are installed to
measure water level, water quality, suspended solid concentration and many other
224
factors. In 1999, all trees in the sub-watershed B were clear-cut. The influence of
this clear cut is examined by analyzing these observed factors.

Figure 12.1 Location of the University Forest in Chiba
WB
SA
SB
BB
WA
GA
GB1
GB3 GB2

Figure 12.2 Fukuroyama-sawa Experimental Watershed
225
12.1.3 Do-sawa Experimental Watershed

Do-sawa Experimental Watershed was established in 1997 to monitor effects
of acid deposition on a natural forest ecosystem. The Do-sawa forest, 8.98 ha in
area, remain untouched since this forest has been declared as the University Forest
in 1898. From the enumeration of trees in the 1970s, the forest has 1,647 trees,
from 42 different species, which are larger than 20cm dbh (183 trees/ha).
The Do-sawa Experimental Watershed (1.37 ha) is equipped by a stilling pool
with a V-notch weir at the outlet of the stream (Kumagae et al, 2000). Water level,
water temperature and electric conductivity are monitored continuously.
Meteorological data including rainfall and rainwater sampling was under taken in
the meteorological observation field in the Fudago Nursery, which has more than
60 years of record.

12.1.4 Shinta Micrometeorological Observation Field

Shinta Meteorological Observation Field was established in 1995 to study on
evapotranspiration from the Japanese cedar forest using a 15 m tower.
Evapotranspiration from a forestland is a phenomenon consists of boundary layer
micro-meteorological and plant physiological processes. From this point of view,
solar radiation, net radiation, wind velocity, air temperature, soil temperature,
humidity and rainfall is measured continuously as micro-meteorological
measurements, whereas sap flow velocity and volume by heat pulse method and
stem heat balance method respectively as plant physiological measurements.

12.2 Rainfall characteristics

The University Forest in Chiba has started meteorological observation in
October 1904 at the Kiyosumi meteorological field. Observations have been
continued even during the WWII until now. As the first step in research
concerning rainfall characteristics in the University Forest, Kuraji et al. (1998)
re-calculated the long-term mean annual rainfall. Ninety-three years daily rainfall
records from 1904 until 1996 were used for re-calculation. The mean annual
rainfall in Kiyosumi Station was found to be 2,282 mm and no significant changes
were detected (Figure 12.3).
226
0
500
1000
1500
2000
2500
3000
3500
1918 1928 1938 1948 1958 1968 1978 1988
A
n
n
u
a
l

R
a
i
n
f
a
l
l

(
m
m
)

Figure 12.3 Long-term records of annual rainfall at Kiyosumi

12.3 Throughfall and stemflow in Japanese Cedar and Cypress Forest

Beneath a forest canopy, rainfall can be partitioned into three fractions:
interception by vegetation; throughfall; and stemflow. Throughfall and stemflow is
an important factor for water budget studies. In Japan, about 10 to 20 % of annual
rainfall is intercepted by forest canopy, and almost a half of the annual
evapotranspiration will be evaporated as the rainfall interception. For input-output
studies of forest, throughfall and stemflow is essential to estimate net atmospheric
input to a watershed. The throughfall and stemflow water quality is different from
that in rainfall due to the condensation, solution of dry deposition and leaching of
leaves and foliage.

12.3.1 Long-term monitoring of throughfall and stemflow

In the Fukuroyamasawa A and Do-sawa Watershed, throughfall and stemflow
volume were monitored for more than 4 years. In the Fukuroyamasawa A
Watershed, an area of mature Chamaecyparis obtusa forest with 70-year old trees
were selected for intensive study of throughfall, stemflow, interception and
associated chemistry. Enumeration of Chanaecyparis obtusa trees, in the
Fukuroyamasawa Experimental Catchment, was done in 1995 and the results
227
showed a density of 932 trees per hectare, a mean diameter at breast height (DBH)
of 21.5cm, and a mean tree height of 19.1 m.
The annual and seasonal water balances of the study plot reported by Kuraji et
al. (1998) is shown in Table 12.1 and Figure 12.4, respectively. The fraction of
stemflow in this forest was about 12% of rainfall on an annual basis, which was
almost the same as the fraction of rainfall interception. Rainfall interception was
larger in the 1996/97 period than the 1995/96 period although rainfall in the
former period was smaller than in the latter. The number of rainfall events in
1996/97, however, was larger than in 1995/96. Two heavy rainfall events occurred
in this period: July 8-11, 1996 (401.0 mm) and September 22, 1996 (401.8 mm by
typhoon 9612). As shown in Figure 3, the monthly rainfall, throughfall and
stemflow in July and September, 1996 was large but the rainfall interception was
not. These results suggest that the interception loss in this forest may be dependent
upon the number of rain events rather than the actual rainfall amount.

0
100
200
300
400
500
600
700
Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep
(mm)
Throughfall
Stemflow
Rainfall Interception
1995 1997 1996

Figure 12.4 Monthly water balance of the study forest during a two year period.
228
Table 12.1 Water balance of the study forest for two individual years (Kuraji et al,
2001). Proportions of throughfall, stemflow and interception to rainfall are shown
in parentheses.
Period Rainfall Number
of events
Throughfall Stemflow Rainfall
Interception
1995.10.2
1996.10.1
2156.4 81 1645.1(76%) 259.9(12%) 258.9(12%)
1996.10.2
1997.10.1
1862.9 95 1365.8(74%) 219.3(12%) 270.2(14%)

Little rainfall interception was observed in winter (December-February) and
August, both periods with little rain. The small rainfall interception with plenty of
rainfall in January and February 1997 may be a result of decreases in
evapotranspiration in winter, as by Ford and Deans (1978) in a 14-year-old Picea
sitchensis in Scotland.

12.3.2 Spatial distribution of throughfall

Tanaka et al. (1998) examine factors determining the spatial distribution of
throughfall by analyzing the results of continuous observations over two and a half
years at 20 fixed through fall collectors in Fukuroyamasawa. They found that the
coefficient of variation of throughfall, among 20 collectors for a single rainfall,
tends to increase for smaller rainfall event, but there are also some rain events that
have small rainfall amount but low coefficient of variation. They found that these
rain events occurred under strong wind speed condition, suggesting that
throughfall in this forest were spatially evenly distributed under strong wind
condition.

12.3.3 Factors affecting stemflow volume and chemistry

Kuraji et al. (1996) showed that the stemflow volume in a rainfall event with
a strong wind condition was larger than that with a weak wind condition and vice
versa for all observed trees in this forest. The throughfall volume was
complementarily related to the stemflow volume. No clear differences in stemflow
volume were detected between Japanese cedar and cypress trees with same dbh
suggesting that the stemflow may produce at the tree stem rather than leaves and
229
branches. The mean dbh of the cedar trees in the study area (29.3 cm) was larger
than that of the cypress trees (21.5 cm). The stemflow volume of a cedar tree, with
the mean dbh, would be about twice as much as that of a cypress tree with the
mean dbh.

12.4 Streamwater

12.4.1 Water balance and hydrological characteristics

The water balance of the Fukuroyamasawa Experimental Watersheds (A, B
and C) was reported by Shiraki et al (1999). From Sep. 1993 to Aug.1996, the
maximum and minimum continuous twelve-month precipitations were 2298.6 mm
and 1502.6 mm respectively. The maximum and minimum continuous
twelve-month runoff were 924.6 mm and 421.7 mm in the A watershed, and 873.1
mm and 413.4 mm in the B watershed, respectively.

12.4.2 Effect of logging on streamflow and stream water chemistry

In the B catchment, runoff volume increased during and after clear-cutting
(Figure 12.5).
NO
3
-
concentration of the B catchment streamwater before clear-cutting was
almost zero and lower than that of A catchment (Figure 12.5). The B catchment
has thick saturated groundwater around the GB2 point where denitrification may
occur. Low concentration of NO
3
-
in the GB2 groundwater may affect the low
concentration of streamwater in the B catchment.
NO
3
-
concentration of the B catchment streamwater during 6 months after
clear-cutting was nearly same range with that of the A catchment (10-100 eq/l).
From November 1999, NO
3
-
concentration in the B streamwater rose to very high
value (200-300 eq/l). During dry spells, the concentration decreased as the runoff
rate decreased.
230

Rainfall
0 00 0
50 50 50 50
100 100 100 100
150 150 150 150
m
m
/
d
a
y
m
m
/
d
a
y
m
m
/
d
a
y
m
m
/
d
a
y
0 00 0
200 200 200 200
400 400 400 400
600 600 600 600
800 800 800 800
e
q
/
l
e
q
/
l
e
q
/
l
e
q
/
l
A
B
0 00 0
2 22 200 00 00 00
4 44 400 00 00 00
6 66 600 00 00 00
8 88 800 00 00 00
e
q
/
l
e
q
/
l
e
q
/
l
e
q
/
l
GA
GB1
GB2
GB3
0 00 0
2 22 20 00 00 00 0
4 44 40 00 00 00 0
6 66 60 00 00 00 0
8 88 80 00 00 00 0
9 99 98 88 8- -- -0 00 04 44 4 9 99 99 99 9- -- -0 00 04 44 4 0 00 00 00 0- -- -0 00 04 44 4
e
q
/
l
e
q
/
l
e
q
/
l
e
q
/
l
10cm
20cm
30cm
60cm
Streamwater NO
3
-
Runoff
0 00 0. .. . 001 001 001 001
0 00 0. .. . 01 01 01 01
0 00 0. .. . 1 11 1
1 11 1
10 10 10 10
100 100 100 100
m
m
/
d
a
y
m
m
/
d
a
y
m
m
/
d
a
y
m
m
/
d
a
y
A
B
Groundwater NO
3
-
Soil water NO
3
-

Figure 12.5 Seasonal variation in rainfall, runoff, NO
3
-
concentration of
streamwater, groundwater and soil water
231

NO
3
-
concentration of groundwater at GB1 point was almost same with that of
catchment B streamwater (Figure 12.6). The concentration of groundwater at GB2
point tended to be lower than that at GB1 point, maybe due to denitrification
around GB2 groundwater. The groundwater at GB3 was rarely observed and the
NO
3
-
concentration was the highest.
The increase in NO
3
-
concentration was at first occurred in the shallow (10-20
cm) soil water (Figure 12.6). NO
3
-
concentration of soil water was higher than that of
groundwater for a year just after clear-cutting but lowered after that. The soil
water sampling point (SB) was just near the GB2 point and the soil water may also
affected by denitrification.
Annual export and input-output budget of NO
3
-
-N from the clear-cut
catchment were about 4 times and 9 times higher than that from the control
catchment, respectively (Table 12.2).

(1500) (1000) (500) 0 500 1000 1500
Throughfall
Stemflow
Soil water SA-10
Soil water SA-20
Groundwater GA
Streamwater A
Mean ion concentration (eq/l)
Cl-
NO3-
SO42-
Na+
NH4+
K+
Mg2+
Ca2+
(1500) (1000) (500) 0 500 1000 1500
Rainfall
Soil water SB-10
Soil water SB-20
Groundwater GB3
Groundwater GB2
Groundwater GB1
Streamwater B
Mean ion concentration (eq/l)
Cl-
NO3-
SO42-
Na+
NH4+
K+
Mg2+
Ca2+

Figure 12.6 Mean solute concentrations of water in the catchment A and B
232
Almost 50 % of runoff volume occurred during high runoff range (above 1.0 mm/hour)
(Figure 12.7). The frequency of high flow was only 1% of the total time of one year. The NO
3
-

concentration of this watershed increases as the runoff rate increase. As a result, about 60 %
of NO
3
-
-N load occurred during the short-term storm event.
These results indicate that the measurement of runoff volume and NO
3
-

concentration during stormflow is essential to estimate annual mass output of
NO
3
-
-N.

Table 12.2 Annual input-output budgets after clear-cut (Nov.1999 - Oct.2000)
kg/ha/year
Rainfall
Throughfall
plus
stemflow
Stream
flow
Input-
output
budgets
NO
3
-N A - 5.6 9.2 -3.6
B 3.4 - 37.5 -34.0
NH
4
-N A - 6.6 0.0 6.6
B 2.4 - 0.0 2.4
Catchment

0% 20% 40% 60% 80% 100%
1 0.1 1 0.05 0.1 0.05
NO
3
-N flux
mm/hour
Frequency
Runoff
Amount
Runoff range

Figure 12.7 Discharge rate and NO3-N flux at Watershed B after clear-cut
(Nov.1999 - Oct.2000)

233
References

Kuraji K., Yamanaka C., Nagashima T., Karukome T. and Norisada M. Rainfall
characteristics in the Kiyosumi Range of Boso Peninsula (I) mean annual
rainfall in Kiyosumi , Bull. Tokyo Univ. Forest, 99, 235-243, 1998 (in
Japanese with English summary)
Kuraji K., Tanaka N., Shiraki K., Karakama I. and Ohta T. Effects of windspeed
on stemflow volume in a mature Cryptomeria japonica and Chamaecyparis
obtusa stand, J. Japan For. Sci. 79, 215-221, 1997 (in Japanese with English
summary)
Kuraji K., Tanaka Y., Tanaka N. and Karakama Y. Genertion of stemflow volume
and chemistry in a mature Japanese cypress forest, Hydrol. Proc., 15,
1967-1978, 2001
Shiraki K., Water balance in the Fukuroyamasawa Experimental Watersheds in
University Forest in Chiba, The University of Tokyo, Bull. Tokyo Univ. Forest,
102, 71-86, 1999 (in Japanese with English summary)
Tanaka N., Kuraji K., Adachi Y. and Ohta T. Factors determining the spatial
distribution characteristics of throughfall. Extended Abstract Volume of
IUFRO Division 8 Conference Proceedings, Kyoto, Japan, 67-68, 1998.
Osaka K., Kuraji K. and Suzuki M. (submitted) Effect of watershed-scale forest
clear-cut on stream water chemistry especially on NO3 concentration.
Manuscript submitted to the J. Japan Soc. Hydrol. Wat. Res. (in Japanese with
English summary)
Kumagae A., Tsukagoshi T., Tanaka Y. and Kuraji K., Changes of stream chemical
characteristics of stream water in small mountainous watersheds, Bull. Tokyo
Univ. Forest, 103, 1-20, 2000.
University Forest in Chiba Visitors guide for University Forest in Chiba,
Graduate School of Agricultural and Life Sciences, The University of Tokyo,
21pp, 2001.

Methods of sampling, measurements and data acquisition for hydrogen and oxygen
isotopic composition in rainwater
235

Methods of sampling, measurements and data acquisition for
hydrogen and oxygen isotopic composition in rainwater

13.1 Introduction

The main purpose of this chapter is to assist participants to understand what
they should mind during sampling of rainwater, such as how to measure
isotopic composition of rainwater, how to convert and standardize the raw data
to conventional delta-formed isotope value.
During water sampling and their storage, isotope fractionation effect is the
most influential factor to make original value changed. Section 13.2 describes
practical methods of field sampling, storage of samples and simulation
experiments in laboratory for understanding the mechanism and process of
isotope fractionation effect during evaporation-condensation and freezing.
Although participants may not be able to measure isotopic composition of
their samples by themselves because of the lack of time, they can learn
principles and procedures in detail for mass-spectrometric analysis in Section
13.3. Isotopic data of the samples can be converted to delta-formed value by
the method described in Section 13.4 for reference. On the last day of training
course, participants will be given time for analysis, discussion and
presentation so that they can deepen their knowledge of the role of hydrogen
and oxygen isotopes in hydrology suggested in lectures and practices.
Although the simulation experiments are simple ones, care should be taken
to avoid an injury, burn, or frostbite when handling glassware, hot water or
dry ice.
Chapter13
236
13.2 Sampling

13.2.1 Technical Procedure for cumulative sampling of precipitation for
isotopic analyses

Original article of this section is derived from the guideline for rainwater
sampling by International Atomic Energy Agency (IAEA), with modification
by authors of this section.
To obtain reliable isotopic data from rain, it is essential that the sampling
procedure described below should be followed in detail. Above all,
evaporation should be avoided, because this strongly affects the isotopic
composition of the water sample. Thus, if a cumulative sample is being
obtained, the rainwater that accumulates in the collector prior to sampling at
the end of each interval should be protected with oil against evaporation with
oil. It is, therefore, essential to use air-tight bottles to preserve, ship or store
precipitation samples collected for isotopic analysis. It is also advisable to use
the high-density polyethylene bottles provided by IAEA, which has been
checked for their tightness and the consistency of isotopic measurements after
several months of storage. The bottles provided by IAEA have a volume of 0.5
litter (for tritium analysis) and 50 ml (for stable isotope analysis), which are
considered the optimal amounts of water required for isotopic analysis. Below
are the procedures that must be followed:
Each sample must represent the cumulative precipitation for a certain period
(e.g. a month), beginning on the first day of the period and continuing until the
end of the period. The amount of rain stored during the period should be
recorded using the rain gauge that normally is set up nearby the rain collector.
In the absence of a rain gauge, the amount of rain can also be determined as
follows: total amount (in litter) of rainwater collected in the vessel, measured
in a graduated cylinder / area of funnel (in m
2
). The resulting value already
represents the amount of precipitation in mm. It is important to know the
corresponding amount of rain (in mm) to be able to calculate the weighed
isotopic value of rainfall.
The rainwater is collected through a funnel in a plastic vessel, called rain
sampler (Fig. 13.1), which is left in an open space for the whole period. The
vessel can be a recycled but very clean plastic container found in chemical
labs. It is advisable to use those with built-in faucets to facilitate sampling at
the end of the period. The sampler is completely covered with cap to avoid
evaporation. It is necessary to put oil, in the rain sampler to prevent
237
evaporation of the accumulating water. The oil layer floating over the water
should have a thickness of about 0.5 cm. The tip of the funnel should not
touch the upper surface of the oil layer. This set-up can be protected by a
fence and raised (ca. 1 meter) from the ground.
At the end of the period, the stored rainwater must be recovered with
following procedures illustrated below. The sampler should not be shaken
aggressively to prevent oil to form an emulsion with water, as it is difficult to
separate. The operations described above should be carried out as rapidly as
possible, in order to reduce the time during which the sample is exposed to the
atmosphere and thus the risk of evaporation.

Fig. 13.1 Rain Sampler
Cap
C CC Co oo oll ll ll lle ee ec cc ct tt ti ii io oo on n n n
B BB Bo oo ott tt tt ttl ll le ee e

Fig. 13.1 Rain Sampler
Cap
Chapter13
238
Equipments
6ml glass bottle

Oil Bottle (30ml)

Special Syringe

Syringe Filter

Waste oil bottle

Cleaning pole

Measure cup (250ml, 100ml)

paper
Gum ring
239
Preparation procedure

Fully mix in the collection bottle

Transfer Rain water and oil into the measure cup

Measure water volume (unit ml)

100ml
90ml
70ml
81.8m
Oil
Sample
Water
Fill in water volume on
the data sheet
Chapter13
240
Take the water sample using special syringe

Attached syringe filter to special syringe

O OO Oil il il il
S SS Sa aa am mm mp pp pl ll le e e e
W WW Wa aa at tt te ee er rr r
O OO Oil il il il
S SS Sa aa am mm mp pp pl ll le e e e
W WW Wa aa at tt te ee er rr r
241

Transfer the water sample into 6ml glass bottle

Label the date and point!

Clean up the collection bottle

Paper
6 66 6m mm ml l l l g gg gl ll la aa ass ss ss ss B BB Bo oo ott tt tt ttl ll le e e e
Push!
Chapter13
242

Pour oil into collection Bottle

Set up the rain collector

Transfer oil in the measure cup into waste oil bottle

Throw away remaining sample water
Waste oil Bottle
Oil Bottle (50ml)
Cap
243

Wipe the measure cup by clean pole

Dry up completely!

Fill in information on the data sheet

Storage of sampled water
When bottled water is stored, always ensure to secure with double cap
tightly. There should be no sharp objects in the box (e.g. screws, nails, wood
splinters) when samples are sent to the lab for analyse. Otherwise, these can
puncture the plastic bottles.

13.2.2 An example for simulating evaporation-condensation and freezing
processes by laboratory experiment

13.2.2.1 Simulating the model of the Rayleigh distillation

Method

(a) Materials
Three neck flask (2 L volume) with two ground-glass* stoppers
Connecting pipe with ground joint*
Dimroth condenser with ground joint*
Measuring cylinder (500 ml volume)
Chapter13
244
Rubber or silicone tube
Mantle heater
Pipette
Sample vials
Zeolite
Laboratory stands
Laboratory jacks
Clamps
Vinyl tapes

*Ground glass joint is chosen to avoid leak of water vapour and to facilitate
the handling. Take care not to damage the joint.

(b) Set up
Set up the materials as shown in Fig. 13.2. Support the flask and condenser
firmly using laboratory jacks, clamps, and a stand. Measure 1 L of water by
the cylinder and put it into the flask through the side neck. At the same time,
take 3 ml of the water as initial (not distillated) sample into a sample vial and
store in a similar manner described in (c). Put the stopper on the flask after
adding a few pieces of zeolite in order to avoid bumping of boiling water.
Flow cooling water so that the water vapour flows upward in the spiral tube
will be condensed in the condenser.

(c) Sampling
Heat the flask by switching on the mantle heater. It will be about 30 minutes
before the boiling and distillation begin. In the mean time, prepare sample
vials and piece of vinyl tapes. Choose one procedure from the followings (It is
confusing to operate both of the procedures at the same time and it may give
some complicated results because of perturbation of the system by frequent
sampling).

ProcedureA: sampling of distilled water
Monitor the volume of total distillated water by measuring cylinder. At
about 100 ml interval, take ca. 3 ml of distillate into the vial by replacing the
measuring cylinder with a sample vial. Immediately screw the cap of the vial
tightly and wind a piece of vinyl tape round the neck of the vial in order to
avoid evaporation during storage. Read the total distillated volume at the
sampling time and fill it in Table 13.1 together with sample identification
245
number that should be written on the tape pasted on the vial. If the measuring
cylinder becomes full (volume of 500 ml) throw away the water. Stop the
experiment when total distillated volume reaches 900 ml. After cooling,
measure the volume of water left in the flask.

Procedure-B: sampling of the residual water
Monitor the volume of total distillated water by measuring cylinder. At
about 100 ml interval take off the stopper on the side neck of the flask and
take ca. 3 ml of residual water in the flask into the vial by using the pipette
(Be careful of the hot water vapour!). Immediately screw the cap of the vial
tightly and wind a piece of vinyl tape round the neck of the vial in order to
avoid evaporation during storage. Read the total distillated volume at the
sampling time and fill it in Table 1 together with sample identification number
that should be written on the tape pasted on the vial. If the measuring cylinder
becomes full (volume of 500 ml) throw away the water. Stop the experiment
when total distillated volume reaches 900 ml. After cooling, measure the
volume of water left in the flask.

(d) Isotopic analysis
Isotopic compositions of the samples are measured at the laboratory of the
Tokyo Institute of Technology, and the data (either hydrogen or oxygen
isotopic compositions, or both of them depending on the number of samples
and available time) are given on the date of discussion. Detailed description of
procedures is given in Section 13.3 and 13.4, and some of them may be shown
during the training course.

Results and remarks
(a) Plot delta values of the samples against f on a sheet of graph paper. As the
evaporation of the water progresses, what happens to the isotopic composition
of distilled or residual water?
(b) Plot the data against lnf. The data will lie on a line. Consider the meaning
of the slope of the regression line and the intercept of y-axis.
(c) Compare the fractionation factor you obtained with that in the literature
(see Chapters 1 and 2). If there is some difference, consider the reason.
(d) This experiment was performed at 100C. Consider how the isotopic
composition would change when the water in the flask or vial is kept at room
temperature without any stoppers.

Chapter13
246

Fig. 13.2 Apparatus for the evaporation-condensation experiment
247
Table 13.1. Data sheet for the evaporation-condensation experiment.

Procedure: A or B

Sample
number
1)

V
(ml)
2)

f
3)
D ()
4)

18
O ()
4)
Comments

1) Assign identification number of the sample and fill it in the wrapped tape
to avoid confusion in isotopic measurement (e.g., group #1-1).
2) Total distilled volume at the time of sampling. Note that the loss of water
at each sampling should be taken into account for detailed analysis of the
results (Compare the volume of water left in the flask after the experiment
with that expected).
3) Fraction of the residual water in the flask relative to the initial volume
[=(1000-V)/1000].
4) Calculate from the raw data obtained by mass-spectrometric
measurements.

Chapter13
248
13.2.3 An example for simulating freezing processes by laboratory
experiment

The isotope fractionation for deuterium and oxygen-18 in water can be
occurred with phase change. So the glacier ice had experienced melting and
refreezing should have the different relationship between D and
18
O from
the Meteoric Water Line, D = 8
18
O + 10 (see Chapter 2). It can be known
from the slope of regression line on a D-
18
O diagram whether glacier ice has
been melting or not.

13.2.3.1 Method

(a) Materials
Centrifuge tube made of polypropylene (50ml)
Heat insulating material (In this time we use styrene form.)
Dial scale
Flask (50ml)
Sample vial (5ml)
Vinyl bag with wire
Water (200ml)
Eyeleteer
Measuring cylinder
Dry Ice

(b) Set up
Measure 50 ml water by measuring cylinder into three centrifuge tubes and
close their screw caps. At the same time, take 5ml of initial water sample.
Bury the Centrifuge tube in the position surrounded by heat insulator and
cover with crushed dry ice as shown in Fig.13.3.

(c) Sampling
After 90 minutes take one centrifuge tube out from the setting. Draw out
remained liquid water from the centrifuge tube through make a hole with
eyeleteer to pre-weighed 50ml flask. And measure its weight (so the weight of
ice will be determined). Take 5ml of the water into the vial. At the same time
put the centrifuge tube with ice into a vinyl bag. When the ice melts perfectly,
take the 5ml of the melting water into the vial. Immediately screw the cap of
the vial tightly and wind a piece of vinyl tape round the neck of the vial in
249
order to avoid evaporation during storage.
Carry out the above work after 100 minutes and 150 minutes and take the
samples.

(d) Isotope analysis
See Section 13.3 and 13.4.

Fig. 13.3 Apparatus for the freezing experiment
Chapter13
250
13.3 Measurement

13.3.1 Principle of mass spectrometry

To measure stable isotopic composition for hydrogen and oxygen in natural
water, isotope ratio mass spectrometry (IRMS) is usually used. The basis of
IRMS is to bend a beam of charged molecules in a magnetic field into a
spectrum of masses (Fig. 13.3). The beam of charged molecules is usually
generated by ionising a gaseous sample at the ion source.
In 1947, Alfred Nier developed the first dual-inlet, double-collector
gas-source mass spectrometer with sector-type magnetic field (Nier, 1947).
The double-collector allowed the simultaneous measurement of two isotopes
and the dual-inlet allowed ratio measurement on both a sample and a reference
by alternating between inlets. Gas source IRMS has since become the
measurement technique of preference for isotopic composition of most of the
light elements (e.g. H, C, N, O and S) because of its relative simplicity and
because the use of international standards allows comparison of databases
from different laboratories. Recent IRMSs have three or more collectors
(multi-collector system), which allow simultaneous measurements of three
major isotopes for CO
2
analysis and of two major isotopes for H
2
analysis. The
IRMS used in this training course is Finnigan MAT 252 (Thermo Quest K.K.)
with CO
2
& H
2
equilibration device (see Fig. 13.5 and 13.6).
251

M
a
s
s
4
6
M
a
s
s
4
5 M
a
s
s
4
4
Reference H2
Waste line
Sample
Preparation
Device
Flight Tube/Magnet
M
a
ss
3
M
a
s
s
2
positively charged ion beams
26.5
o
26.5
o
Ion Source
Ion Accelerator &
Beam Focussing
Electron Trap
Ionizing Filament
Detector cups
Repellar
Variable Volume
Variable Volume
Reference CO2
Inlet System

Fig. 13.4 Schematic diagram of dual-inlet IRMS with water equilibration
device
Chapter13
252

Fig. 13.5 Photograph of the Isotope Ratio Mass Spectrometry (Finnigan
MAT 252 at Tokyo Institute of Technology)

253

Fig. 13.6 Photograph of the equilibration device at Tokyo Institute of
Technology

Chapter13
254
A heated tungsten-coated iridium (thoria) filament, inside the ion source
block cavity, ionises a laminar stream of gas entering the ultra-high vacuum
source (Fig. 13.4). The gas molecules are stripped off one electron by the
electron impact (EI), producing positive ions (e.g. CO
2
+
) that are then
accelerated through a voltage gradient and focused into the flight tube upon
exiting the source. Positively charged molecules obtain the velocity as

eV mv
2
2
1
Eq. (13-1)

where m, v, e and V represent mass of the charged molecules, obtained
velocity, electrical charge and accelerating voltage, respectively.
The ionisation efficiency varies between 0.01 and 0.1% for different
instruments. The ion beam bends as it passes through the field of a magnet
installed over the flight tube. Here, the beam separates into a spectrum of
masses according to the isotopes present as

Hev
r
mv
2
Eq. (13-2)

where r and H represent curvature radius of the ion orbit and the force of
magnetic field, respectively. Using Eq. (13-1) and Eq. (13-2), the following Eq.
(13-3) can be obtained.

V
H r
e
m
2
2 2
Eq. (13-3)

When the force of magnetic field H and accelerating voltage V are held
constant, curvature radius r is only varied with mass of the ion.
Each mass beam continues to the ion detectors where preset faraday cup
collectors measure each ion current. By collecting two or three ion beams
simultaneously, the ion currents can be expressed as mass ratios. CO
2
would
contribute three principal peaks at mass 44 (
12
C
16
O
2
), 45 (
13
C
16
O
2
or
12
C
17
O
16
O) and 46 (
12
C
18
O
16
O). H
2
would contribute two principal peaks at
mass 2 (
1
H
1
H) and 3 (
2
D
1
H). A dual-inlet system allows the mass spectrometer
255
to measure ratios in the sample and the reference alternately. Thus, the
extreme fractionation imparted during ionisation in the source is resolved.

13.3.2 Analytical methods for hydrogen and oxygen isotopes

Mass spectrometers do not like water, which is a sticky gas and loves to
condense throughout the high vacuum inlet and ion source (Clark and Fritz,
1997). Consequently, both hydrogen and oxygen isotopic composition in water
must be measured in another form of molecule except for water, which are H
2

and CO
2
, respectively. Up-to-date preparation techniques and their precisions
for both isotopes are described in this section.

13.3.2.1 Hydrogen isotope

To determine hydrogen isotopic composition of water, there are two
conventional concepts. One is the reduction method that water converted to
hydrogen gas (H
2
) using metallic uranium (Bigeleisen et al., 1952) or metallic
zinc (Coleman et al., 1982), and the other is the equilibrium method that water
equilibrated with H
2
gas using Pt catalyst (Rolston et al., 1976; see equation
below.). Equilibrium method is usually used for multi-sample and/or
automated analysis.

H D HO H H H HO D
1 2 1 1
Pt
1 1 1 2

The equipment used in this course for equilibration can set twenty-four
sample bottles at the single run. Usually, six working standards and three
running standards, for estimating the error at each run, are measured with
sample waters. Therefore, we can measure fifteen samples at single run.
Isotopic compositions of working standards were determined by international
standards (e.g. SMOW; see also Section 13.4 for detail) prior to routine
analysis for samples. The running standard is used for checking whether all
measurements at single run are successfully completed and for comparing with
previous runs.

13.3.2.2 Oxygen isotope

To determine oxygen isotopic composition of water, the equilibrium method
Chapter13
256
is usually used. In this method, CO
2
that are isotopically equilibrated to
sample water are measured instead of water themselves. Between CO
2
and
water, there is an isotope exchange reaction as follows, which achieves
equilibration easily.

O O C
2
1
O H O C
2
1
O H
16 18 16
2 2
16 18
2

The oxygen isotope distribution between water and CO
2
in above reaction is
controlled by temperature. Therefore, reaction temperature must be held
constant through each of runs including sample and working standards.
The equipment for oxygen isotope analysis is identical to hydrogen analysis,
except for Pt catalyst.

13.3.2.3 Basic procedures for isotope analyses by equilibrium methods

To obtain both hydrogen and oxygen isotopic composition from same water
samples, hydrogen isotope should be measured first because Pt catalyst as
easily oxidized. The basic procedures for both isotope analyses by equilibrium
methods are as follows:

1) Put catalyst into equilibrium vials, that must be dried up, put 1 ml water
sample into them and set them to the equilibration device ASAP to avoid
evaporation.
2) Pump these vials into vacuum for 2 minutes and verify significant leakage.
3) After that, pump up remaining gas for 2 minutes again, fill them with H
2

gas up to around half of atmospheric pressure and shake them for 2
minutes to purge any dissolved gases.
4) After that, pump up for 2 minutes again and refill them with H
2
as
equilibration gas.
5) Shake all vials in the thermostatic water bath (180.01C) at over 1 hour to
achieve isotope equilibration between water and H
2
gas.
6) Introduce reference H
2
gas to IRMS for tuning condition of the ion source.
7) Measure isotopic composition of both equilibrated H
2
gas with water and
reference gas. Each of samples (include working and running standard) is
measured seven times for both sample and reference and averaged them. It
will take 9 hours to complete 24 samples.
257
8) After finishing hydrogen measurements, repeat 2)
9) After that, pump up for 2 minutes again, fill them with CO
2
gas up to
around half of atmospheric pressure and shake them 2 minutes to purge
any dissolved gases.
10) After that, pump up for 2 minutes again and refill them with CO
2
as
equilibration gas.
11) Shake all vials in the thermostatic water bath (180.01C) at over 9 hour to
achieve isotope equilibration between water and CO
2
gas.
12) Introduce reference CO
2
gas to IRMS for tuning condition of the ion
source.
13) Measure isotopic composition of both equilibrated CO
2
gas with water and
reference gas. Each of samples (include working and running standard) is
measured seven times for both sample and reference and averaged them. It
will take 9 hours to complete 24 samples.

13.3.3 H
3
factor

In the case of measuring hydrogen isotopic composition, a particular
correction that called H
3
factor correction must be needed. For hydrogen
isotope, mass 2 and mass 3 are measured as described above. There are two
isotope species in mass 3,
1
H
2
D and
1
H
1
H
1
H, which is produced in ion source
by the collapse of H
2
molecule as follows.

H H H H

3 2 2

The reaction constant for H
3
is controlled by the pressure of H
2
. If H
2
amount
>>HD or H
3
, apparent mass ratio (i
3
/i
2
) detected by each faraday cup (mass 2
and mass 3) is described as

2
2 2
3
H
ki
H
HD
i
i
Eq. (13-4)

meas cor
Eq. (13-5)

Chapter13
258
2 2
3
H
HD
i
i
Eq. (13-6)

where k,
cor
and
meas
are the reaction constant for H
3
, delta value after and
before correction (raw data), respectively.
Actually, the H
3
factor correction is usually operated by the computer
automatically, but every trainees or users must keep their mind on this.

13.4 Data processing

13.4.1 How to convert raw data to the delta value

13.4.1.1 Standards

As described in Section 13.3, stable isotopic composition of water is
determined relative to standard. This relative difference is reported as a delta
value (), which is defined as

sample
= [R
sample
/R
standard
- 1] 1000

where R
sample
represents isotopic composition of water sample (D/H,
O-18/O-16) and R
standard
is the corresponding ratio of the standard. Since the
ratio difference is multiplied by 1000, have units of parts per thousand (per
mil, ).
Standards for isotope analysis are assigned the value of zero per mil on the
-scale of interest. Ideally, standards would be homogeneous materials, with
isotopic compositions similar to those of samples undergoing investigation,
that is available in large quantity, easy to distribute, and easy to handle for
chemical preparation and isotopic analysis. Unfortunately, this ideal has been
rarely attained, and many important materials are either inhomogeneous or are
no longer available. Nevertheless, useful isotopic standard materials are
distributed by the International Atomic Energy Agency (IAEA) and the
National Institute of Standards and Technology (NIST), and others are
available commercially.
At present two of standards are internationally accepted for oxygen isotope,
i.e. VSMOW and PDB. The VSMOW (Vienna Standard Mean Ocean Water)
259
is water, distributed by the IAEA. The isotopic composition of VSMOW is
close to the average ocean water. Thus, it is used in all hydrologic
investigations and it is relevant to use in this course. On the other hand, PDB
(Pee Dee Belemnite) is a fossil carbonate from the Pee Dee Formation of
South Carolina (U.S.A.). Its utility is primary for paleoenvironmental studies.
The O-18 content of VSMOW is practically identical to the SMOW
previously defined by Craig (1961) to be (1993.42.5)10
-6
as the absolute
isotopic abundances. Baertschi (1976) measured the absolute isotopic
abundances of O-18 in VSMOW and reported (2005.20.45)10
-6
.
Besides VSMOW, an O-18-poor sample, called SLAP (Standard Light
Arctic Precipitation), is distributed by the IAEA. The
18
O value for SLAP
relative to VSMOW were defined by the IAEA as
18
O
SLAP/VSMOW
= -55.5
(Gonfiantiti, 1978).
These international standards are also used for hydrogen isotope analysis.
Craig (1961) determined the absolute isotopic abundances of D in SMOW to
be (1582)10
-6
. Hageman et al. (1970) measured the absolute isotopic
abundances of D in VSMOW and reported to be (155.760.05)10
-6
. The D
values for SLAP relative to VSMOW were determined by the IAEA as D

SLAP/VSMOW
= -428 (Gonfiantiti, 1978).

13.4.1.2 Correction by SMOW/SLAP scale
For hydrogen isotopic composition measurement, water sample have to be
prepared by equilibrating a reference H
2
gas with the water sample. The D/H
ratio for the equilibrated H
2
gas derived from the water sample is measured
relative to a reference H
2
gas. Since the results represent D value to a
reference H
2
gas, those have to be corrected to SMOW-SLAP scale using
working standards.
For the correction to SMOW-SLAP scale, D value for working standards
to SMOW (D
WS/SMOW
) has to be known at first. For this purpose, D values
for SMOW, SLAP and working standards are measured simultaneously
relative to the reference H
2
gas and then the D
WS/SMOW
value is calculated
from following:

D
WS/SMOW
= (R
WS
/R
SMOW
-1) 10
3
f
=[(D
WS/REF
10
-3
+1) / (D
SMOW/REF
10
-3
+ 1) - 1] 10
3
f

where D
WS/REF
and D
SMOW/REF
are D values for working standards and
SMOW measured relative to the reference H
2
gas, respectively. Depending on
Chapter13
260
the apparatus used for measurements, D value for SLAP relative to SMOW
(D
SLAP/SMOW
) would slightly different from the recommended value (-428).
f is a factor for the correction of this difference and is given by following:

f = (D
SLAP/SMOW
)
definition
/ (D
SLAP/SMOW
)
measured
= -428 / {[(D
SLAP/REF
10
-3
+1) / (D
SMOW/REF
10
-3
+1) -1] 10
3
}

Using the D
WS/REF
value, D values for samples relative to SMOW
(D
sample/SMOW
) are determined as following:

D
sample/SMOW
= (R
sample
/R
WS
R
WS
/R
SMOW
-1) 10
3

= [(D
sample/WS
10
-3
+1) (D
WS/SMOW
10
-3
+1) -1] 10
3

D
sample/WS
is calculated from D
sample/REF
value and D
WS/REF
value obtained
by the simultaneous measurement, as following.

D
sample/WS
= (R
sample
/R
REF
R
REF
/R
WS
-1) 10
3

= [(D
sample/REF
10
-3
+1) / (D
WS/REF
10
-3
+1) -1] 10
3

At TITECH (Tokyo Institute of Technology), two working standards are
used. One is the distilled oceanic water obtained from sea surface of the
Kuroshio Current (DKW: Distilled Kuroshio Water) and the other is the
meltwater from ice obtained from Antarctic ice cap (DOME). D values for
these working standards to SMOW are 1.49 and 396.58 for DKW and
DOME, respectively. These working standards are also used for the
calculation of the f values (F value) instead of SMOW and SLAP as following:

(D
DOME/DKW
)
SMOW
= [(D
DOME/SMOW
10
-3
+1) / (D
DKW/SMOW
10
-3
+1) -1] 10
3
= -395.
7

F = (D
(DOME/DKW)/SMOW
)
definition
/(D
(DOME/DKW)/SMOW
)
measured

= -395.
7
/ {[(D
DOME/REF
10
-3
+1) / (D
DKW/REF
10
-3
+1) -1] 10
3
}

Then the determination of D values for samples to SMOW (D
sample/SMOW
) is
the following.

D
sample/SMOW
= (R
sample
/R
DKW
R
DKW
/R
SMOW
-1) 10
3

= [(D
sample/DKW
10
-3
+1) (D
DKW/SMOW
10
-3
+1) -1] 10
3

261

where D
sample/DKW
is calculated from D
sample/REF
value and D
DKW/REF
value
obtained by the simultaneous measurement as following.

D
sample/DKW
= (R
sample
/R
REF
R
REF
/R
DKW
-1) 10
3
F
= [(D
sample/REF
10
-3
+1) / (D
DKW/REF
10
-3
+1) -1] 10
3
F

Definition of technical terms used in Chapter 13

Gases
Reference gas
CO
2
or H
2
gas to introduce standard (ST) side of mass spectrometer
Equilibration gas
CO
2
or H
2
gas to introduce equilibration device and be equilibrium
isotopically with sample water

Standards (water)
International standard
Isotope standards distributed by the International Atomic Energy
Agency (IAEA) and the National Institute of Standards and
Technology (NIST). Usually, values must be noted relative to Vienna
Standard Mean Ocean Water (VSMOW) and/or Standard Light Arctic
Precipitation (SLAP) for hydrogen and oxygen isotopic composition
of water.
Working standard
For routine analysis, working standards determined by international
standards are used. Following standards should be prepared to obtain
accurate results.
1. Meltwater of snow which has values close to SLAP for both
isotopes.
2. Seawater (i.e. values close to SMOW)
Running standard
Land or rain water which has values between SMOW and SLAP to check the
day-to-day reproducibility of data.
Chapter13
262
References

Baertschi, P., Absolute
18
O content of Standard Mean Ocean Water. Earth
Planet. Sci. Lett., 31, 341-344, 1976.
Bigeleisen, J. et al., Conversion of hydrogenic materials to hydrogen for
isotopic analysis. Anal. Chem., 24, 1356-1357, 1952.
Clark and Fritz, Environmental Isotopes in Hydrogeology, Lewis Publishers,
New York, pp. 328, 1997.
Coleman, M.L. et al., Reduction of water with zinc for hydrogen isotope
analysis., Anal. Chem., 54, 993-995, 1982.
Craig, H., Standard for reporting concentrations of deuterium and oxygen-18
in natural water. Science, 133, 1833-1834, 1961.
Gonfiantiti, R., Standards for stable isotope measurements in natural
compounds. Nature, 271, 534-536, 1978.
Hageman, R., Nief, G. and Roth, E., Absolute isotopic scale for deuterium
analysis of natural waters. Absolute D/H ratio for SMOW. Tellus, 22,
712-715, 1970.
IAEA, Technical Procedure for cumulative monthly sampling of precipitation
for isotopic analysis. pp. 2, 1997.
Nier, Rev. Sci. Instr., 18, 398, 1947.
Rolston, J.H. et al., The deuterium isotope separation factor between hydrogen
and liquid water. J. Phys. Chem., 80, 1064-1067, 1976.

Part II

Outline of the Training Course
in 2001
265
Outline
As a part of the Japanese contribution to the International Hydrological
Programme (IHP), a short course for participants from the Asia-Pacific region is going to
be conducted on hydrogen and oxygen isotopes in hydrology, from 9 to 22 September,
2001, at the Institute for Hydrospheric-Atmospheric Sciences, Nagoya University,
Nagoya, at Volcanic Fluid Research Center, Tokyo Institute of Technology, Kusatsu, at
the University Forest in Chiba, the University of Tokyo, Chiba, and at Department of
Environmental Science and Technology, Tokyo Institute of Technology, Yokohama,
Japan. The course includes a series of lectures in English, practice sessions and technical
tours of various research institutions and facilities concerned with isotope hydrology.

Objectives
The general aim of the IHP short course is to help participants develop their basic
knowledge of hydrological systems and of their sensitivity to climatic changes, as well as
to contribute to solving current global environmental problems. Stable isotopes of
hydrogen and oxygen, and tritium of hydrological waters, have been used to trace water
circulation in various scale in time and space. They have been revealed to be good
parameters for understanding the hydrological systems and solving the hydrological
problems. Fundamentals for sampling, determination, data analysis, and transport models
of water isotopes will be briefly lectured about seawater, water vapour, precipitation water,
snow, ice, surface water, soil water, ground water, and volcanic and hydrothermal water.
Participants can get comprehensive idea of the application of hydrogen and oxygen
isotopes in hydrology by practice to collect various kinds of hydrological samples,
determine their isotope ratios, and analyse their data by themselves.

Course Contents (convenor: N. Yoshida)
Lecturers
O. Abe (Institute for Hydrospheric-Atmospheric Sciences, Nagoya University)
K. Kuraji (Department of Environmental Science and Technology, Tokyo Institute of
Technology)
M. Kusakabe (Institute for Study of the Earth's Interior, Okayama University)
O. Matsubaya (Research Institute of Materials and Resources, Akita University)
M. Nakawo (Institute for Hydrospheric-Atmospheric Sciences, Nagoya University)
A. Numaguti (Graduate School of Environmental Earth Science, Hokkaido University)
T. Ohba (Volcanic Fluid Research Center, Tokyo Institute of Technology)
H. Satake (Department of Environmental Biology and Chemistry, Toyama University)
J. Shimada (Department of Earth Science, Kumamoto University)
A. Sugimoto (Center for Ecological Research, Kyoto University)
S. Toyoda (Department of Environmental Chemistry and Engineering, Tokyo Institute
of Technology)
M. Tsujimura (Hydrology Laboratory, Institute of Geoscience, University of Tsukuba)
H. Wushiki (Japan International Cooperation Agency)
K. Yamada (Department of Environmental Chemistry and Engineering, Tokyo Institute
of Technology)
M. Yasuhara (Environmental Geology Division, Geological Survey of Japan)
266
N. Yoshida (Department of Environmental Science and Technology, Tokyo Institute of
Technology)

Lectures
L1 Fundamentals of hydrogen and oxygen isotopes in hydrology ............. N. Yoshida
Stable and radioactive isotopes of light elements, and natural abundance of isotopes
Equilibrium and kinetic fractionation of isotopes, and decay of radioactive isotopes
Determination of stable isotope abundance

L2 General feature on the hydrogen and oxygen isotopic ratios of natural water
.............................................. O. Matsubaya
Basic technical terms, relationship among natural waters, and homogeneity of sea water
Meteoric water, Craig's relation, Dansgaard's relation, d-value and kinetic evaporation
Meteoric precipitation, Rayleigh process, Dansgaard's four effects
Surface water and groundwater, catchment area of river.

L3 Large-scale transport of water vapor and isotope variability .......... A. Numaguti
Large-scale atmospheric circulation and water budget
Large-scale distribution of D & O-18 in precipitation and its variability
Large-scale water transport and D & O-18 variability
Isotope circulation model and its application

L4 Water circulation in regional scale ....................................................... A. Sugimoto
Structure of clouds and temporal variation in the isotopic compositions of precipitation
Cloud type, and factors controlling the isotopic compositions of precipitation
Water cycles in ecosystems, fate of rainwater, and water uptake by plants

L5 Isotopes in snow and ice ........................................................................... M. Nakawo
Diffusion process in snow and ice; Isotope process in ice and water system;
Fractionation during dry and wet snow metamorphism
Isotope data in ice cores (in Greenland, Antarctica, and mid-latitude)

L6 Tritium in precipitation and surface waters ............................................ H. Satake
Measurement of tritium
Tritium in precipitation
Tritium in river and groundwater

L7 Stable isotopic composition in soil water ............................................ M. Tsujimura
Role of soil water in water cycle, and physical processes of soil water movement
Soil water extraction techniques, suction, centrifugation, and distillation
Processes leading to isotopic variations in soil water, and water budget

L8 Environmental isotopes in groundwaters ............................................. M. Yasuhara
Where, when, and how groundwater is recharged
Groundwater mixing
267
Palaeo-groundwaters

L9 Use of environmental isotope tracers to reveal groundwater flow system .
.................................................. J. Shimada
Groundwater flow system study with some application of the effect of tunnel
construction
Groundwater recharge process revealed by soil tritium profiles
Use of several environmental tracers to detect the surface and subsurface water
interaction
L10 Water in arid lands.. .............................................................................. H. Wushiki
Precipitation, river and lake water in arid area
Groundwater, and isotopic application to water resources development
Field themes remained for further investigation

L11 Volcanic and hydrothermal waters ................................................... M. Kusakabe
Hot spring waters and geothermal waters
Volcanic, magmatic and mantle waters

Practices
Field studies and laboratory experiments

P1 Sampling of fluids involved in hydrothermal system .................................T. Ohba
Various water samples will be taken around Mt. Kusatsu-Shirane.
Geothermal fluid: Property of geothermal fluid; Apparatus of the sampling;
Measurements
Volcanic gas; Property of volcanic gas; Apparatus of the sampling; Measurements
Crater lake water: Property of active crater lake water; Apparatus of the sampling;
Measurements
Hot spring water: Property of hot spring water; Apparatus of the sampling;
Measurements

P2 Hydrological and hydrochemical characteristics of rainfall, throughfall, stemflow
.................................................... K. Kuraji
Various water samples will be taken in the University Forest in Chiba.
Rainfall: Long-term records; Temporal and spatial distribution; Chemistry
Throughfall and stemflow in a natural Abies (Momi) and Tsuga forest and Japanese
Ceder and Cypress forest; Long-term monitoring of throughfall and stemflow; Spatial
distribution of throughfall; Factors affecting stemflow volume and chemistry
Streamwater; Water balance and hydrological characteristics; Long-term monitoring of
streamwater chemistry; Effect of logging on streamwater chemistry; Groundwater and
soil water chemistry

P3 Methods of sampling, measurement and data processing for hydrogen and
oxygen isotopic composition in rainwater....................................O. Abe, S. Toyoda,
268
K. Yamada, N. Kurita, S. Hashimoto, R. Uemura and N. Yoshida
All procedures for hydrogen and oxygen isotopic composition in rainwater will be
shown.
Water samples collected will be analyzed at the isotope laboratory in Tokyo Institute of
Technology.
Sampling: Equipment; An example for simulating evaporation-condensation processes
by laboratory experiments
Measurement: Principle of mass-spectrometer; Sample preparation; Determination of
isotope ratios by isotope equilibration methods
Data processing: How to convert raw data to the delta value

Schedule (9-22 September, 2001)
9 (Sunday)
Sept., 2001
Arrival at Nagoya Stay in Nagoya
10 (Monday) Guidance, Lectures 1, 2 & 3, Icebreaker reception at
Nagoya University
Stay in Nagoya
11 (Tuesday) Lectures 4, 5 &11, laboratory tour at IHAS, Nagoya
University
Stay in Nagoya
12
(Wednesday)
Move to Volcanic Fluid Research Center, Tokyo Institute
of Technology at Kusatsu-Shirane
Stay in Kusatsu
13 (Thursday) Lecture and Practice1, Sampling of hydrothermal water
etc. and laboratory tour at the Center
Stay in Kusatsu
14 (Friday) Move to Tokyo Stay in Tokyo
15 (Saturday) Lectures 6, 7, 8 & 9 at National Olympics Memorial
Youth Center
Stay in Tokyo
16 (Sunday) Lecture10 & Lecture and Practice 3 Stay in Tokyo
17 (Monday) Move to Chiba Experimental Forest, University of Tokyo,
Lecture and Practice 2, Sampling of stream water etc.
Stay in Chiba
18 (Tuesday) Move to Tokyo, Lecture and Practice 3 (contd) Stay in Tokyo
19
(Wednesday)
Lecture and Practice 3 (contd), Measurement of samples
at Yokohama Campus of Tokyo Institute of Technology
Stay in Tokyo
20 (Thursday) Lecture and Practice 3 (contd), Simulation training, and
Discussion
Stay in Tokyo
21 (Friday) Closing ceremony, Free time Stay in Tokyo
22 (Saturday) Departure from Narita Air Port

Part III

Past Activities of the IHP
Training Course

271
Past activities of the IHP Training Course (1991-2000)

The IHP Training Course in Asia and the Pacific Region has been
executed since 1991 by the Working Group for IHP Training Course, under the
direction of the Sub-Committee for IHP, Japanese National Commission for
UNESCO. The Training Course was aimed at giving participants an
opportunity to learn observation technology of hydrology and to have practical
experience in hydrological observation in the field.
In the First to Sixth-sessions of the Training Course, the training began
with two or three preliminary lectures to introduce the subjects to be studied
throughout the remainder of the course schedule. After this introduction,
students have been taken around to several specialized institutes in the days
following, to hear about what was actually done there, and to see modern
instrumentation in general hydrology. It has been found, however, that this
training approach possibly encourages passiveness on a part of the students
because they spend an inordinate amount of time traveling daily to the host
institutions where they can only listen and observe rather than participate
actively.
Some innovations, therefore, were made at the Seventh-session, both in
the educational content and in the schedule. Firstly, we decided to focus the
training course on more clearly defined targets, and the first years programme
concentrated on Snow Hydrology. Secondly, we decided to include practice
sessions such as a field programme to allow the students, themselves, the
opportunity to carry out experiments and make relevant observations/analyses.
Finally, we decided to prepare a newly edited textbook for the participants in
the training course.

272
1. The First IHP Training Course, 1991
1.1 Participants
Ms. Zhao Ling (China), Student of the Special Program of Sciences of
Atmosphere and Hydrosphere, Graduate School of Science, Nagoya
Univ., Japan
Mr. Zhao Jing (China), ibid.
Ms. Hidajat Bernadia Irawati Tjandradewi (Indonesia), ibid.
Mr. Geng Biao (China), Student of Sciences of Atmosphere and
Hydrosphere, Graduate School of Science, Nagoya Univ., Japan
Ms. Sri Mulat Yuningsih (Indonesia), Res. Inst. for Water
Mr. Roslan Bin Sahat (Malaysia), Resources Development, Dept. of
Public Works Hydrology Branch, Dept. of Drainage and Irrigation
1.2 Schedule and Lectures
Mar. 2 3 Water Res. Inst., Nagoya Univ. (Nagoya)
Lecture on runoff processes in river watersheds (Prof. F.
Takagi, Water Res. Inst., Nagoya Univ.)
Lecture and practice session on precipitation and water
resources in Asia (Assoc. Prof. Y. Fujiyoshi, Asst.. Prof.
K. Kato, Assoc. Prof. Y. Ishizaka, Water Res. Inst.
Nagoya Univ.)
Lecture and practice session on the matter cycle and water
quality in the hydrosphere (Prof. M. Sakamoto, Prof. N.
Handa, Assoc. Prof. K. Ohta, Water Res. Inst., Nagoya
Univ.)
Mar. 4 6 Chubu Regional Construction Bureau, Min. of Construction
(Chubu Region)
Technical tour of hydrological facilities for river control
Mar. 7- 8 (Sat-Sun): holidays
Mar. 9 Water Resources Res. Center, Disaster Prevention Res. Inst.,
Kyoto Univ.
Laboratory experiment on evaporation from bare soil
Mar.10 Kiryu Experimental Catchment, Faculty of Agriculture,
Kyoto Univ.

273
Meteorological and hydrological observations at a small
catchment in hilly terrain
Mar. 11 (Kyoto to Tsukuba)
Mar. 12 Forestry & Forest Products Res. Inst., Min. of Agriculture,
Forestry & Fisheries (Hitachi-Ohta)
Training on evaporation and soil moisture measurements,
and hydrological observation
Mar.13 National Inst. for Environmental Studies, Environment
Agency (Tsukuba)
Technical tour of research facilities for water quality
conservation
Mar. 14-15 (Sat-Sun): holidays
Mar. 16-17 Public Works Res. Inst., Min. of Construction (Tsukuba)
Lectures on hydrological observations and models of water
discharge
Mar.18 Forecast Dept. & Observation Dept., Japan Meteorological
Agency (Tokyo)
Lecture and technical tour concerning short-range
precipitation forecasting using radar and the AMeDAS
(automated meteorological data acquisition system)
Mar. 19 Meteorological Satellite Center, Japan Meteorological
Agency (Kiyose)
Technical tour of Meteorological Satellite Center

2. The Second IHP Training Course, 1992
2.1 Participants
Ms. Thapa, Arati (Nepal), Student of Special Program of Sciences of
Atmosphere and Hydrosphere, Graduate School of Science, Nagoya
Univ., Japan
Mr. Kayastha, Rijan Bhakta (Nepal), ibid.
Mr. Sarwono, Pitoyo Sudibyo (Indonesia), ibid.
Mr. Le Cong Thanh (Vietnam), ibid.
Mr. Xu Guangxiang (China), ibid.

274
Mr. Adisak, Suriyavanagul (Thailand), Electricity Generating Authority
Mr. Pham Van Tan (Vietnam), Network Operation Dept.,
Hydrometeorological Service
Mr. Ekanayaka M. Wimalasena (Sri Lanka), Investigation Section,
National Water Supply and Drainage Board
Mr. S. Mahmoud Borghei (Iran), Asst.. Prof., Dept. of Civil Engineering,
Sharif Univ. of Technology
Mar. 1- 2 Water Res. Inst., Nagoya Univ. (Nagoya)
Lecture and practice session on precipitation and water
resources in Asia (Asst. Prof. T. Ohta, Asst.. Prof. K. Kato,
Assoc. Prof. Y. Ishizaka, Water Res. Inst., Nagoya Univ.)
Lecture and practice session on the material cycle and
water quality in the hydrosphere (Assoc. Prof. H. Terai,
Water Res. Inst., Nagoya Univ.)
Technical tour
Mar. 3- 5 Kanto Regional Construction Bureau, Min. of Construction
(Nagoya to Tokyo, Kanto Region)
Mar. 6- 7 (Sat-Sun): holidays
Mar. 8- 9 Environmental Res. Center, Univ. of Tsukuba (Tsukuba)
Observation and data analysis of evapotranspiration
Mar. 10-11 National Res. Inst. for Earth Science & Disaster Prevention,
Science & Technology Agency (Tsukuba-Ichihara, Chiba)
Laboratory experiment of rainfall
Technical tour of an experimental hydrological catchment
Mar. 12-14 (Fri-Sun): holidays
Mar. 15-16 National Res. Inst. of Agricultural Engineering, Min. of
Agriculture, Forestry & Fisheries (Tsukuba)
Analysis of irrigation and drainage
Study of experimental ground water facilities
Mar. 17 Forecast Dept. & Observation Dept., Japan Meteorological
Agency (Tokyo)
Lecture and technical tour for short-range precipitation
forecasting using radar and the AMeDAS
Agency (Kiyose)

275

3. The Third IHP Training Course, 1993
3.1 Participants
Mr. Kamal, Md. Syeeduzzaman (Bangladesh), Student of the Special
Program of Sciences of Atmosphere and Hydrosphere, Graduate
School of Science, Nagoya Univ., Japan
Ms. Sipayung, Sinta Berliana (Indonesia), ibid.
Ms. He Kaiqing (China), ibid.
Mr. Zhu Yan (China), Dept. of Hydrology, Hohai Univ.
Mr. Wu Yongxiang (China), Nanjing Inst. of Hydrology & Water
Resources, Min. of Water Resources
Ms. Suva, Imelda Manalastas (Philippines), Bureau of Res. & Standards,
Dept. of Public Works & Highways
Mr. Dwivedi, Ashok Kumar (India), Hydrological Investigations Division,
National Inst. of Hydrology, Roorkee
Mr. Ahmad, Bashir (Pakistan), Centre of Excellence in Water Resources
Engineering, Univ. of Engineering & Technology, Lahore
Aug. 16-17 Institute for Hydrospheric-Atmospheric Sciences (IHAS),
Nagoya Univ. (Nagoya)
Lectures on multi-scale cloud distributions in monsoon
regions of Asia (Asst. Prof. K. Kato)
Lectures on cloud physics and chemistry in climate
studies (Prof. H. Tanaka)
Lectures on Asian cryosphere and changes in water
resources (Prof. Y. Ageta)
Lectures on water cycle and stable isotopes (Assoc. Prof. M.
Nakawo)
Aug. 18-20 Chubu Regional Construction Bureau, Min. of Construction
(Chubu Region)
Aug. 21-22 (Sat-Sun): holidays

276
Aug. 23 Water Resources Res. Center, Disaster Prevention Res. Inst.,
Kyoto Univ.
Lecture on control of run-off water
Aug. 24 Kiryu Experimental Catchment, Faculty of Agriculture,
Kyoto Univ.
Meteorological and hydrological observations at a small
catchment in hilly terrain
Aug. 25 (Kyoto to Tsukuba)
Aug. 26 Forestry & Forest Products Res. Inst., Min. of Agriculture,
Forestry & Fisheries (Hitachi-Ohta)
Training on evaporation and soil moisture measurements,
and hydrological observation
Aug. 27 Public Works Res. Inst., Min. of Construction (Tsukuba)
discharge
discharge
Aug. 31 National Inst. for Environmental Studies, Environment
Agency (Tsukuba)
conservation
Sep. 1 Meteorological Satellite Center, Japan Meteorological
Agency (Kiyose)
Sep. 2 Forecast Dept. & Observation Dept., Japan Meteorological
Agency (Tokyo)

277
4. The Fourth IHP Training Course, 1994
4.1 Participants
Mr. Sunil Adhikary (Nepal), Student of the Special Program of Sciences
of Atmosphere and Hydrosphere, Graduate School of Science,
Nagoya Univ., Japan
Mr. Zhang Wan Chang (China), ibid.
Mr. Mohammad Rezwanul Islam (Bangladesh), ibid.
Mr. Birbal Rana (Nepal), Student of Sciences of Atmosphere and
Ms. Y.K. Handapangoda (Sri Lanka), Teaching Asst.. in Civil Engineering,
Univ. of Peradeniya, Peradeniya
Ms. Byambaagiin Oyunchimeg (Mongolia), Min. of Nature and
Environment, Inst. of Water Problems, Ulaan Baatar
Mr. M. Fakhruddin (Indonesia), Puslitbang Limnology, LIPI, Bogor
Ms. Gadis Sri Haryani Bengen (Indonesia), Res. and Development Center
for Limnology, Indonesian Inst. of Sciences, Bogor
Aug. 15-16 IHAS, Nagoya Univ. (Nagoya)
Lecture on Asian monsoon and water cycle (Asst. Prof. K.
Kato)
Lecture on carbon cycling with water cycle (Prof. N.
Handa)
Lecture on aquatic micro-organisms and water quality
(Assoc. Prof. H. Terai)
Aug. 17-19 Kanto Regional Construction Bureau, Min. of Construction
(Nagoya to Tokyo, Kanto Region)
Aug. 22-23 Environmental Res. Center, Univ. of Tsukuba (Tsukuba)
Observation and data analysis of evapotranspiration
Aug. 24-25 National Res. Inst. of Agricultural Engineering, Min. of
Study of experimental facilities for ground water

278
Aug. 26 National Inst. for Environmental Studies, Environment
Agency (Tsukuba)
Technical tour of Res. facilities for water quality conservation
Aug. 29-30 National Res. Inst. for Earth Science & Disaster Prevention,
Science & Technology Agency (Tsukuba-Chiba Pref.)
Large scale rainfall experiment
Technical tour of an experimental hydrological catchment
Aug. 31 Forecast Dept. & Observation Dept., Japan Meteorological
Agency (Tokyo)
Sep. 1 Meteorological Satellite Center, Japan Meteorological Agency
(Kiyose)

5. The Fifth IHP Training Course, 1995
5.1 Participants
Ms. Meng Xiao (China), Student of the Special Program of Sciences of
Atmosphere and Hydrosphere, Graduate School of Sciences,
Nagoya Univ., Japan
Mr. Talukder Abul Bashar MD. Alauddin (Bangladesh), ibid.
Mr. Liu Jing Shi (China), ibid.
Mr. Begkhutod Perapol (Thailand), ibid.
Mr. Bhatt Maya Prakash (Nepal), ibid.
Mr. Ma Xieyao (China), Student of Sciences of Atmosphere and
<Part 1: Chubu Region>
Dec. 13-15 Chubu Regional Construction Bureau, Min. of Construction
(Aichi and Gifu)
<Part 2: Kinki Region>

279
Feb. 13 Lake Biwa Res. Inst., Shiga Pref. (Otsu)
Lecture and technical tour for Lake Biwa
Feb. 14 Branch Office of Kinki District of Public Works, Min. of
Construction (Otsu)
Lecture and technical tour for mountain conservation
Dept. of Forestry, Kyoto Univ. (Otsu)
Lecture and technical tour of an experimental basin
Feb. 15 Disaster Prevention Res. Inst., Kyoto Univ. (Uji)
Lecture and technical tour on disaster prevention
Hirakata Operation Center, Min. of Construction (Hirakata)
Lecture on river water control
Feb. 16 Section of River Management, Kyoto Pref. (Kyoto)
Technical tour concerning river management
<Part 3: Kanto Region>
Mar. 11 Inst. for Forestry and Forest Products, Min. of Agriculture,
Forestry and Fisheries (Hitachi-Ohta)
Training on evaporation and soil moisture measurement,
and on making hydrological observation
Mar. 12 National Inst. for Environmental Studies, Environment
Agency (Tsukuba)
conservation
Mar. 13 Public Works Res. Inst., Min. of Construction (Tsukuba)
Lecture on hydrological observation and models of water
discharge
Mar. 14 Forecast Dept. & Observation Dept., Japan Meteorological
Agency (Tokyo)
Agency (Kiyose)

280
6. The Sixth IHP Training Course on Snow Hydrology, 1996
6.1 Participants
Mr. Zulkefle bin Ghazali (Malaysia), Hydrology Division, Dept. of
Irrigation and Drainage
Mr. Rhoel C. Villa (Philippines), National Hydraulic Res. Center, U.P.
College of Engineering
Mr. Luong Tuan Anh (Vietnam), Inst. of Meteorology and Hydrology,
Hanoi Hydrometeorological Service of Vietnam
Mr. Atthaporn Buddhapolit (Thailand), Hydrology Division, Royal
Irrigation Dept.
Ms. Rungkarn Krishnamra (Thailand), Soil and Water Conservation
Division, Land Development Dept.
Aug. 19-20 IHAS, Nagoya Univ. (Nagoya)
Lecture on hydrological characteristics of tropical forests
(Prof. K. Kuraji, Univ. of Tokyo)
Lecture on remote sensing from space (Prof. K.
Nakamura, IHAS, Nagoya Univ.)
Lecture on development of distributed rainfall-runoff
model by using digital elevation models (Prof. Y.
Tachikawa, Kyoto Univ.)
Lecture on the new thrust of IHP activities in Southeast
Asia and Pacific, Asian/Pacific FRIEND (Flow Regimes
from International Experimental and Network Data)(Prof.
K. Takeuchi, Yamanashi Univ.)
Aug. 21-23 Kanto Regional Construction Bureau, Min. of Construction
(Kanto Region)
Aug. 26-27 Environmental Res. Center, Tsukuba Univ. (Tsukuba)
Lecture and practice session on evapotranspiration
measurements
Lecture on the role of the biosphere for climate systems

281
Aug. 28-29 National Res. Inst. of Agricultural Engineering, Min. of
Technical tour to an irrigated paddy field
conservation
Aug. 31-Sep. 1 (Sat-Sun): holidays
Sep. 2-3 National Res. Inst. for Earth Science & Disaster Prevention,
Environment Agency (Chiba Pref.)
Large-scale rainfall experiment
Technical tour to the hydrological catchment basin
Sep. 4 Forecast Dept. & Observation Dept., Japan Meteorological
Agency (Tokyo)
Sep. 5 Meteorological Satellite Center, Japan Meteorological
Agency (Kiyose)

7. The Seventh IHP Training Course on Snow Hydrology,
1998

The general aim of the IHP short course is to help participants
develop their basic knowledge of hydrological systems and of their
sensitivity to climate changes as well as to contribute to solving current
global environmental problems. The cryosphere is most vulnerable to the
projected global warming trend that has recently become a major concern
in many countries. The seventh training course focuses on snow hydrology.
The topics covered range from basic knowledge of the role of the
cryosphere in the global environment to technical applications, including
observations and measurements in snow packs.

282
7.1 Participants
Mr. D. B. Ch ettri (Bhutan), Executive Engineer, Meteorology Unit, Div.
Power, Min. of Trade and Industry
Mr. Liang, Zhongmin (China), Teacher, Dept. Hydrology, Hohai Univ.
Mr. Om Ratna Bajracharya (Nepal), Senior Hydrologist, Dept. Hydrology
and Meteorology, Min. of Science and Technology
Mr. Shiva Bhakta Prajapati (Nepal), Hydrologist, Dept. Hydrology and
Meteorology, Min. of Science and Technology
Mr. Aurangzeb Khattak (Pakistan), Asst. Director, WRRC
Mr. Edvin Aldrian (Indonesia), M2, IHP Student, IHAS, Nagoya Univ.
Mr. Dang Xuan Phong (Vietnam), M2, IHP Student, IHAS, Nagoya Univ.,
Japan
Mr. Li, Jianjun (China), M2, IHP Student, IHAS, Nagoya Univ., Japan
Mr. Yudi Iman Tauhid (Indonesia), M2, IHP Student, IHAS, Nagoya Univ.,
Japan
Mr. Bhuwan Chandra Bhatt (Nepal), M1, IHP Student, IHAS Nagoya
Univ., Japan
Mr. Zhou Shiqiao(China), M1, IHP Student, IHAS Nagoya Univ., Japan
Mr. Kayastha Rijan Bhakta (Nepal), Res. Fellow, IHAS Nagoya Univ.,
Japan
Mr. Suresh Chandra Pradhan (Nepal), Hydrological Asst., Dept.
Hydrology and Meteorology, Min. of Science and Technology
Mr. Keshav Raj Sharma (Nepal), Hydrological Asst., Dept. Hydrology and
Meteorology, Min. of Science and Technology
Mr. Chok Bahadur Gurung (Nepal), Hydrological Asst., Dept. Hydrology
and Meteorology, Min. of Science and Technology
Dr. Dorji Wangdu, Head (Bhutan), Division of Geology and Mines
Ms. Diraagiin Erdenetsetseg (Mongolia), Expert, Centre for Climate and
Environmental Change, Inst. of Meteorology and Hydrology
Mr. Nozomu Naito (Japan), D3, Graduate Student, IHAS Nagoya Univ.
Mr. Fumio Nakazawa (Japan), M1, Graduate Student, IHAS Nagoya Univ.
Mr. Yosihiro Yoshioka (Japan), M2, Graduate Student, Nagaoka Univ. of
Technology
Lecturers

283
Y. Ageta, IHAS, Nagoya Univ.
T. Aoki, Meteorological Res. Inst.
K. Goto-Azuma, Nagaoka Inst. of Snow and Ice Studies, National Res.
Inst. for Earth Science and Disaster Prevention
N. Hayakawa, Dept. of Civil and Environmental Engineering, Nagaoka
Univ. of Technology
H. Iida, Sediment Control Division, Dept. of Civil Engineering, Toyama
Prefectural Government
I. Kamiishi, Centre of Snow and Ice Technology, ARGOS Co. Ltd.
S. Kobayashi, Res. Inst. for Hazards in Snowy Areas, Niigata Univ.
M. Lu, Dept. of Civil and Environmental Engineering, Nagaoka Univ. of
Technology
H. Mizuno, Meteorological College
M. Nakawo, IHAS, Nagoya Univ.
H. Ohno, Japan International Res. Centre for Agricultural Sciences
K. Satow, Civil Engineering, Nagaoka National College of Technology
T. Takeda, IHAS, Nagoya Univ.
Y. Takeuchi, Nagaoka Inst. of Snow and Ice Studies, National Res. Inst.
for Earth Sciences and Disaster Prevention
K. Yokoyama, Hokuriku National Agricultural Experiment Station

Schedule (9 March, 1998 - 22 March, 1998)
Mar. 9 Arrival at Nagoya, Japan
Mar. 10 (IHAS, Nagoya Univ.)
Guidance
Lecture on glaciers and the water cycle
Lecture on precipitation process
Lecture on synoptic conditions and snow fall precipitation
process
Icebreaker reception in the evening
Mar. 11 (IHAS, Nagoya Univ.)
Technical tour
Move from Nagoya to Myoko (4 hour train ride)
Mar. 12 Lecture on water circulation over the earth: the roles of
snow and ice
Radiation processes and remote sensing of snow
Practice session for spectral albedo observations on a
snowfield
Mar. 13 Lecture on snowmelt hydrology

284
Practice session for hydrographical observations
Fabrication of the Endo-type snow-water content meter (1)
Mar. 14 Lecture on metamorphism of deposited snow
Lecture on snow changes in snow pack and melt water
chemistry during snowmelt
Lecture on heat budget of a snow pack
Mar. 15 Technical bus tour to
Niigata Experiment Laboratory, Public Works Res. Inst.,
Tohkamachi Experiment Station, Forestry and Forest
Products Res. Inst., Nagaoka Inst. of Snow and Ice Studies,
National Res. Inst. for Earth Science and Disaster
Prevention (Stay overnight at a spa, Yomogihira Hot
Spring, in the snowy region)
Mar. 16 Technical bus tour continues to Myoken Weir, Shinano
River
Facilities for snow removal by melting in Nagaoka City
Shinano River Work Office, Hokuriku Regional
Construction Bureau
Oukouzu Division Work, Shinano River and the Division
Work Museum
Arai Weir, Shinano River
Fabrication of the Endo-type snow-water content meter (2)
Mar. 17 Practice session for heat exchange over a snow surface
Mar. 18 Practice session for snow pit observations
Mar. 19 Data handling exercise (reception in the evening)
Mar. 20 Report preparation
Move from Myoko to Nagoya (train ride)
Mar. 21 Closing ceremony
Mar. 22 Departure from Nagoya

8. The Eighth IHP Training Course on Remote Sensing, 1999

Recently, the environmental problems attracts strong attentions. The
spatial scales of the problems range from very local one to global one.
Environmental problems have close connection to atmospheric and

285
hydrospheric phenomena. For the atmospheric and hydrospheric sciences,
satellite remote sensing is very useful and essential because of its
capability to observe the atmosphere and hydrosphere in a big scale. For
example, recently launched TRMM (Tropical Rainfall Measuring Mission)
is providing us a unique three-dimensional rain structures regardless of the
location over tropical and a part of mid latitude regions. ADEOS
(Advanced Earth Observing Satellite) gave us beautiful images of global
phytoplankton distribution over global ocean.
Ground-based remote sensing which includes radars and lidars is also
useful for the atmospheric observation.
The lectures give the basic theory of remote sensing, technology and
applications, and current Earth observation satellites, etc.
8.1 Participants
Mr. Limsakul Atsamon (Thailand), IHAS, Nagoya Univ., Japan
Ms. Jiang Cuiling (China), IHAS, Nagoya Univ., Japan
Mr. Aryal Deepak (Nepal), IHAS, Nagoya Univ., Japan
Ms. Aranya Fuangswasdi (Thailand), Ground Water Division, Dept. of
Mineral Resources
Ms. Zainab Hashim (Malaysia), Hydrology Division, Dept. of Irrigation
and Drainage
Mr. Wibowo Hendro (Indonesia), Puslitbang Limnologi-LIPI
Dr. Cheng Ming (China), Nanjing Inst. of Hydrology and Water Resources,
Min. of Water Resources
Mr. Te Navuth (Cambodia), Min. of Water Resources and Meteorology
Ms. Yuko Ogawa (Japan), Global Information and Early Warning Service,
Food and Agriculture Organization of the United Nations, Italy
Mr. Thongdum Pengyai (Thailand), Hydrometeorology Division,
Meteorological Dept.
Mr. Chhetri B. Tek (Nepal), IHAS, Nagoya Univ., Japan
Mr. Haryoko Urip (Indonesia), Meteorological and Geophysical Agency
Ms. Li Zhuxiao (China), IHAS, Nagoya Univ., Japan
Lecturers and lecture titles
Y. Honda, Chiba Univ.: Global vegetation observation

286
T. Iguchi, Communications Res. Laboratory (CRL), Min. of Posts and
Telecommunications: Active microwave measurement of rain and
clouds from space I
T. Itabe, Communications Res. Laboratory, Min. of Posts and
Telecommunications: Lidar proving of the atmosphere
K. Kajiwara, Chiba Univ.: Global vegetation observation I
T. Koike, Nagaoka Univ. of Technology: Soil wetness measurement from
satellite microwave remote sensing
T. Kozu, Communications Res. Laboratory, Min. of Posts and
Telecommunications: Active microwave measurement of rain and
clouds from space II
K. Nakamura, IHAS, Nagoya Univ.: Observation of atmosphere by radar
T. Saino, IHAS, Nagoya Univ.: Ocean color observation by satellite
H. Shimoda, Tokai Univ.: Current remote sensing technology for global
warming monitoring
D. Short, IHAS, Nagoya Univ.: The Tropical Rainfall Measuring Mission
K. Tsuboki, IHAS, Nagoya Univ.: Radar measurement of precipitation
processes
S. Uratsuka, Communications Res. Laboratory, Min. of Posts and
Telecommunications: Synthetic aperture radar and its applications
Schedule
Mar. 8 Arrival at Nagoya, Japan
Mar. 9 Guidance, lectures and reception at IHAS, Nagoya Univ.
Mar. 10 Lectures and technical tour in IHAS, Nagoya Univ.
Mar. 11 Lecture and guidance of data analysis training
Mar. 12 Data analysis training
Mar. 13 Data analysis training (continued)
Mar. 14 Move to CRL at Koganei, Tokyo
Mar. 15 Lectures
Mar. 16 Lectures and technical tour at CRL
Mar. 17 Move to Tokai Univ. and lectures/move to Chiba Univ.
Mar. 18 Lectures
Mar. 19 Lectures and move to Nagoya
Mar. 20 Free day
Mar. 21 Departure from Nagoya

287
9. The Ninth IHP Training Course on Limnology,
1999 Summer

Limnology is a field of study on terrestrial water ecosystems such as
lakes, rivers, reservoirs, ground waters and wetland. Human activities
have been linked very closely to those water ecosystems and changed
them directly or indirectly through global environmental changes. We
have to learn basic limnological processes and how to manage and
conserve those water ecosystems with sustainable development through
the next century.
Limnological studies in Japan only began in 1899 and we are
celebrating their centennial history. The following programs have been
prepared to welcome trainees of the IHP training course in limnology in
the summer of 1999.
9.1 Participants
Mr. Abung Rachmann (Indonesia), Res. Inst. for Water Resources
Development
Dr. Arveti Nagaraju (India), Dept. of Geology, Sri Venkateswara Univ.
Dr. Chen Yuanfang (China), College of Water Resources and
Environment, Hohai Univ.
Ms. Daram S. Enkhtsetseg (Mongolia ), Inst. of Meteorology and
Hydrology
Mr. Hossain Md Anawar (Bangladesh), IHP student in IHAS, Nagoya
Univ., Japan
Ms. Lythi M. Hai (Vietnam), Dept. of Water Resources and Environment,
Inst. of Geography
Mr. Mohd. Talha Mohd. Zaharon (Malaysia), Environmental Health
Section, Engineering Services Division, Min. of Health
Ms. Sirisampan Satiraporn (Thailand), IHP student in IHAS, Nagoya
Univ., Japan
Lecturers and lecture titles

288
H. Terai, IHAS, Nagoya Univ.: Material cycling in deep and shallow
water ecosystems
K. Ichino, Faculty of International Communication, Aichi Univ.: Low-cost
water treatment systems using constructed wetlands
T. Yoshioka, IHAS, Nagoya Univ.: Current technology in
limnology (1) Stable isotope ecology
T. Okino, Faculty of Sciences, Shinshu Univ.: A historical review of
limnology in Japan and a case study on Lake Suwa
K. Kato, School of Allied Medical Sciences, Shinshu Univ.: Current
technology in limnology (2) Microbial ecology
T. Hanazato, Suwa Hydrobiological Station, Shinshu Univ.: Global
environment and lake ecosystems
H. Fushimi, School of Environmental Sciences, The Univ. of Shiga Pref.:
Water resources and environmental problems of Lake Biwa
M. Sakamoto, School of Environmental Sciences, The Univ. of Shiga
Pref.: Eutrophication and management of freshwater environments
M. Nakamura, Lake Biwa Res. Inst., Shiga Pref.: Lake Biwa Yodo River
water systems: Evolving issues on integrated management of water
quality
M. Kumagai, Lake Biwa Res. Inst., Shiga Pref.: Ecological in
homogeneity due to dynamic variability in Lake Biwa
T. Nakajima, Lake Biwa Museum, Shiga Pref.: Evolution and distribution
of cyprinid fish in East Asia during Neogene, and formation of the
cyprinid fauna in Lake Biwa
R. F. Walker, Lake Biwa Res. Inst., Shiga Pref.: Current technology in
limnology (3) Algal species classification by image processing
N. Nakamoto, Faculty of Textile Science and Technology, Shinshu Univ.:
Misunderstanding of slow sand filtration in Japan and the
biological mechanism of its system
M. Overmars, UNESCO, Jakarta Office: Special Lecture: Current IHP
activities in Asia Pacific Region
Schedule
Jul. 26 Arrival at Nagoya, Japan
Jul. 27 Guidance and lectures at IHAS (icebreaker reception in the
evening)
Jul. 28 Move to Suwa Hydrobiological Laboratory, guidance and
lecture
Jul. 29 Field trip on Lake Suwa, observation and sampling

289
Jul. 30 Chemical and biological analysis of water and sediment
samples
Jul. 31 Field trip to Lake Shirakoma, observation and sampling
(reception in the evening)
Aug. 1 Technical bus tour to Kurobe Reservoir and Nishina sub
alpine lakes
Aug. 2 Lake Kizaki Laboratory, travel to Hikone by train
Aug. 3 Lecture at the Univ. of Shiga Pref., visit Limnological
Laboratory, move to Otsu
Aug. 4 Lecture and technical tour at Lake Biwa Res. Inst.
Aug. 5 Field trip to Lake Biwa on the research vessel "Hakken"
Aug. 6 Technical tour to Lake Biwa Museum, back to Nagoya
Aug. 7 Closing ceremony and reception
Aug. 8 Departure from Nagoya

10. The Tenth IHP Training Course
on Hydrology related to Head Water Management,
2000 Summer

Head Water Area is understood as both supplying a source of clean
water and Assisting in the prevention of flood/sediment disasters for
living people downstream. Over-cutting of trees or industrial pollution
sometimes damage to the surrounding environment of Head Water.
Japan has experiences such failures 100 years ago. In the training course,
We would like to focus on hydrological impacts of non-vegetation and the
effects of both reforestation in steep slope and erosion control works in
river-bed, in a watersheds damaged in the past with sulphurous acid gas
caused by the refining factory of copper. Lectures are provided at the
Faculty of Technology, Gunma Univ., Kiryu-city, Gunma Pref., and field
training is to be done in the basin of the Watarase River, a tributary of the
Tone River which is very important for Tokyo Metropolitan.

290
10.1 Participants
Mr. Evandri Ahmad (Indonesia), R&D Center for Informatic and
Computer Science
Mr. Suy Sovann (Cambodia), Min. of Water Resources and Meteorology
Mr. Manoloth Soukhanouvong (Lao PDR), Dept. of Meteorology and
Hydrology (DMH) Min. of Agriculture and Forestry
Ms. Stephanie Bowis (New Zealand), West Coast Regional Council
Ms. Ubolwan Jenphanitsub (Thailand), Office of the National Water
Resources Committee The Secretarial of the Prime Minister
Mr. Nguyen Kim Tuyen (Vietnam), Hydrometeorological Service of
Vietnam
Mr. Karma (Bhutan), IHAS, Nagoya Univ., Japan
Mr. Adhikari Birendra Raj (Nepal), IHAS, Nagoya Univ., Japan
Ms. Myagmar Munkhtsetseg (Mongolia), IHAS, Nagoya Univ., Japan
Lecturers
T. Ohta, Graduate School of life and Agriculture, Univ. of Tokyo
S. Kobatake, Faculty of Technology, Gunma Univ.
Y. Fukushima, IHAS, Nagoya Univ.
Y. Kawano, Forestry Agency, Min. of Agriculture
M. Nish, Nikko Branch Office, Min. of Construction
K. Honda, Asian Inst. of Technology, Thailand
T. Tsujimoto, Graduate School of Engineering, Nagoya Univ.
H. Tanji, Inst. for Agricultural Engineering, Min. of Agriculture
H. Kawashima, Graduate school of life and Agriculture, Univ. of Tokyo
G. Takahashi, Toyama Prefectural Univ. of Agriculture

Schedule (July 24 - August 6, 2000)
Jul. 24 Arrival at Narita Airport and move to Kiryu-city
Jul. 25 Guidance and lectures at the campus of Gunma Univ.
Typology of erosion processes and watershed management (T.
Ohta)
Effect of human activities on head water (T. Ohta)
History of mountain devastation in the Watarase River (S.
Kobatake)
Jul. 26 Lecture

291
Hydrological processes in headwater (Y. Fukushima)
Jul. 27 Lecture
Forest conservation project in headwater areas (Y.
Kawano)
Erosion control in Japan (M. Nishi)
Evaluation of erosion control work using remote sensing
and GIS (K. Honda)
Jul. 28 Technical tour to Ashio
Jul. 29 Technical tour to Mt. Nantai
Jul. 30 Inspect sights of Nikko
Jul. 31 Lecture and practice
Runoff analysis of head water (S. Kobatake)
Aug. 1 Lecture and practice
Sediment transport and river management (T. Tsujimoto)
Aug. 2 Technical tour to the integrated Dam Control Office
Aug. 3 Lectures
Irrigation system and watershed management (H. Tanji)
River basin management and water quality (H.
Kawashima)
Watershed management and conservation of ecosystem (G.
Takahashi)
Aug. 4 Technical tour to the Watarase Retarding Basin and Tone-
Oozeki Barrage
Aug. 5 Move to Tokyo
Aug. 6 Departure from Narita

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International Hydrological Programme

Hydrogen and Oxygen Isotopes in Hydrology

12.3 Throughfall and stemflow in Japanese Cedar and Cypress Forest....

-9.5 -9.5 -9.5 -9.5

-100 -110 -120 -130

O values vary in much

O of snowfall observed in Sapporo,

O of snow particles varied with time. Trend

O is also observed, not for all case but often (Fig.

O and D of water vapor and cloud droplets during the adiabatic

O of water vapor decreases because heavy water isotopes tend to enter

O of cloud droplets decreases with height, because

O of water vapor decreases with height (Fig. 3.4).

O were observed for precipitation from a cloud.

O relationship of precipitation is shown in Fig. 3.5. When cloud

O relation. Precipitation particles produced

O observed for the

O. However, the line for D-

O of water vapor and cloud droplets during adiabatic

O values of water vapor and cloud

O relationship in the cloud droplet formed from a water

O values increase due to evaporation.

O relationship changes. The magnitude of isotopic change

O of precipitation particles shows no

O vary spatially. When the cloud

O values of solid particles

Os (c), vertical profiles of

Ov (d) and solid cloud. The

O values are calculated,

O of initial water vapor. Figures are

) and temperature difference

O in the European and African continents, the effect varies

O and -0.25 to -2.6 D per 100m

Environmental isotopes in groundwaters

Environmental isotopes in groundwaters

O diagram, groundwaters plot very close to the

Environmental isotopes in groundwaters

O values in precipitation and monthly mean

O/C (Fig. 7.5).

O values, suggesting an effect of -2.2

Use of environmental isotope tracers to reveal groundwater flow system

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